Particulate wood preservative and method for producing same

ABSTRACT

A wood preservative includes injectable particles comprising one or more sparingly soluble copper salts. The copper-based particles are sufficiently insoluble so as to not be easily removed by leaching but are sufficiently soluble to exhibit toxicity to primary organisms primarily responsible for the decay of the wood. Exemplary particles contain for example copper hydroxide, basic copper carbonate, copper carbonate, basic copper sulfates including particularly tribasic copper sulfate, basic copper nitrates, copper oxychlorides, copper borates, basic copper borates, and mixtures thereof. The particles typically have a size distribution in which at least 50% of particles have a diameter smaller than 0.25 μm, 0.2 μm, or 0.15 μm. At least about 20% and even more than 75% of the weight of the particles may be composed of the substantially crystalline copper salt. Wood or a wood product may be impregnated with copper-based particles of the invention.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional application60/571,535 filed on May 17, 2004, which is incorporated herein byreference, to co-pending U.S. patent application Ser. No. 10/868,967filed Jun. 17, 2004, and to U.S. Provisional Application titled: MILLEDSUBMICRON CHLOROTHALONIL WITH NARROW PARTICLE SIZE DISTRIBUTION, ANDUSES THEREOF, filed on Oct. 8, 2004, which is also incorporated hereinby reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

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INCORPORATION-BY-REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC

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SEQUENCE LISTING

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FIELD OF THE INVENTION

The present invention relates to particulate-based biocidalcompositions, particularly wood preservatives comprising particlesincluding one or more copper compounds. More particularly, the inventionrelates to a method of manufacture of particulate-based biocidalcompositions capable of being injected into wood, the biocidalcompositions, methods of preserving wood using the compositions, andwood treated with the compositions of this invention.

BACKGROUND OF THE INVENTION

Preservatives are used to treat wood to resist insect attack and decay.The commercially used preservatives are separated into three basiccategories, based primarily on the mode of application, into waterborne,creosote, and oil borne preservatives. Waterborne preservatives includechromated copper arsenate (CCA), ammoniacal copper quat, ammoniacalcopper zinc arsenate, and ammoniacal copper arsenate. Wood treated withthese chemicals sometimes turn green or grey-green because of a chemicalreaction between copper in the preservative and the sun's ultravioletrays. The preservatives leach into the soil over time, but the copperamines leach from wood at rates several times those observed for CCA.

The primary preserved wood product has historically been southern pinelumber treated with chromated copper arsenate (CCA). Most of thistreated lumber was used for decks, fencing and landscape timbers. Therehas recently been raised concerns about the safety and health effects ofCCA as a wood preservative, primarily relating to the arsenic contentbut also to the chromium content. In 2003/2004, due in part toregulatory guidelines and to concerns about safety, there has been asubstantial cessation of use of CCA-treated products. A new generationof copper containing wood preservatives use a form of copper that issoluble. Known preservatives include copper alkanolamine complexes,copper polyaspartic acid complex, alkaline copper quaternary, copperazole, copper boron azole, copper bis(dimethyldithiocarbamate),ammoniacal copper citrate, copper citrate, and the copper ethanolaminecarbonate. In practice the principal criteria for commercial acceptance,assuming treatment efficacy, is cost. Of the many copper-aminecompositions listed above, only the copper ethanolamine carbonate andammoniacal copper are in widespread use. There are several problems withthese new copper-amine-containing preservatives.

The soluble copper containing wood preservatives are very leachable,compared to CCA. This leaching is of concern for at least tworeasons: 1) removal of the copper portion of the pesticide from the woodby leaching will compromise the long term efficacy of the formulation,and 2) the leached copper causes concern that the environment will becontaminated. Copper is extremely toxic to certain fish at sub-part permillion levels. One study reported the Synthetic Precipitation LeachingProcedure gave the leachate from CCA-treated wood contained a baselineconcentration of about 4 mg copper per liter; leachate from copper(ammonium) boron azole-treated wood contained seven times the baseline;leachate from copper bis(dimethyldithiocarbamate) treated wood had twicethe baseline concentration; leachate from alkaline copper quaternarytreated wood had over seven times the baseline concentration; andleachate from copper citrate treated wood had over fifteen times thebaseline concentration. Copper leaching is such a problem that somestates do not allow use of wood treated with the soluble coppercontaining wood preservatives near waterways.

The commercial soluble copper containing wood preservatives causeincreased metal corrosion, for example of nails within the wood.Preserved wood products are often used in load-bearing out-doorstructures such as decks. Traditional fastening material, includingaluminum and standard galvanized fittings, are not suitable for use withwood treated with these new preservatives. Many regions are nowspecifying that hardware, e.g., fittings, nails, screws, and fasteners,be either galvanized with 1.85 ounces zinc per square foot (a G-185coating) or require Type 304 stainless steel.

Further, the copper-containing portion of the treatment is notprotective against some biological species, and these soluble coppercontaining wood preservatives require higher copper loading, a secondorganic biocide, or both to be effective. Indeed, we believe the aminesfrom the copper-amine complex encourage the growth of molds,particularly sapstain molds.

Another concern with soluble copper preservative products generally isthat most preservative materials are manufactured at one of severalcentral locations but are used in disparate areas and must be shipped,sometimes substantial distances. The cost of providing and transportingthe liquid carrier for these soluble products can be considerable, andthe likelihood of an extreme biological impact on fish is very high iftransported soluble copper wood preservative material is spilled oraccidentally released near a waterway.

Finally, the cost of the amine—between three and 4 moles of amine arerequired to solubilize a mole of copper) is very high. This applicationproposes wood preservatives which solve each of these problems.

SUMMARY OF THE INVENTION

The principal aspect of the invention is sparingly soluble orsubstantially insoluble, biocidal particulates adapted to beincorporated into as a preservative treatment into wood and woodproducts. The biocide particulates preferably contain one or moresparingly soluble, copper-, zinc- and/or tin-containing particulates.Optionally the biocidal particulates can comprise solid, substantiallyinsoluble organic biocides. Optionally, one or more of the biocidalparticulates can further comprise a permeable coating of a substantiallyinsoluble organic biocide. The biocide particulates of the currentinvention are also advantageously incorporated in nonfouling paints andcoatings. Additionally, the biocide particulates when used in foliarapplications on crops provides an efficacious treatment that is moreresistant to rain, and the amount of the biocide may be reduced comparedto prior art formulations having larger mean particle sizes and widerparticle size distributions.

A first embodiment of this invention is an effective, long-lasting,environmentally responsible, non-staining/coloring, inexpensive,non-corrosion-inducing, injectable, sparingly solublecopper-salt-containing particulate preservative treatment for wood andwood products that is substantially free of hazardous material. As usedherein the term injectable means readily injectable into Southern Pinewood using conditions standard in the industry (e.g., partial vacuum andup to 120 psig) for a distance of at least several inches into the wood.A second embodiment of this invention is an effective, long-lasting,inexpensive, non-corrosion-inducing, micron- to sub-micron-sized,sparingly soluble copper-salt-containing particulates for use innon-fouling paints and coatings, and for use in foliar applications.

A third embodiment of this invention is an effective, long-lasting,environmentally responsible, non-staining/coloring, inexpensive,non-corrosion-inducing, injectable, sparingly solublezinc-salt-containing particulate preservative treatment for wood andwood products that is substantially free of hazardous material. A fourthembodiment of this invention is an effective, long-lasting, inexpensive,non-corrosion-inducing, micron- to sub-micron-sized, sparingly solublezinc-salt-containing particulates for use in non-fouling paints andcoatings, and for use in foliar applications.

Another embodiment of this invention is an effective, long-lasting,environmentally responsible, non-staining/coloring, inexpensive,non-corrosion-inducing, injectable, sparingly solubletin-salt-containing particulate preservative treatment for wood and woodproducts that is substantially free of hazardous material.

A fifth embodiment of this invention is an effective, long-lasting,environmentally responsible, non-staining/coloring, inexpensive,non-corrosion-inducing, injectable, substantially insoluble solidorganic biocide-containing particulate preservative treatment for woodand wood products that is substantially free of hazardous material. Asixth embodiment of this invention is an effective, long-lasting,inexpensive, non-corrosion-inducing, sub-micron-sized, substantiallyinsoluble solid organic biocide-containing particulate for use innon-fouling paints and coatings, and for use in foliar applications. Asused herein, the term “organic biocide” also includes organometallicbiocides. By “substantially insoluble” (or “sparingly soluble” as theterm relates to organic biocides), we mean the organic biocide has asolubility in water of less than about 0.1%, and most preferably lessthan about 0.01%, for example in an amount of between about 0.005 ppmand about 1000 ppm, alternatively between about 0.1 ppm and about 100ppm or between about 0.01 ppm and about 200 ppm.

The copper-containing particles, the zinc-containing particles,tin-containing particles, and the substantially insoluble solid organicbiocide-containing particles can be used independently, but considerablesynergy can be achieved by using these in combinations of two or allthree. In some embodiments, copper(I) oxide and/or zinc oxide may beused to partially or completely replace the sparingly soluble coppersalts and the sparingly soluble zinc salts respectively. Certain coppersalts of organic biocidal materials and copper(I) oxide, and also thesparingly soluble copper salts, are generally referred to ascopper-containing biocidal compounds. Similar terms are used for zinccompounds.

In a preferred embodiment, the copper-containing particulates comprisesparingly soluble copper salts. Exemplary particles comprise for examplecopper hydroxide and optionally a copper oxide. At least about 20%, 30%,50%, or 75% of the weight of the copper-based particles may be composedof the sparingly soluble copper salt. Exemplary copper-containingparticles of the invention are sufficiently small to be injectable intothe wood. For example, substantially all of the copper-containingparticles may be sized to occupy pores or vesicles of wood. In oneembodiment, exemplary wood preservatives comprise copper-containingparticles having a size distribution in which at least 50% of particleshave a diameter smaller than 0.25 microns, 0.2 microns, or 0.15 microns.That particular characteristic, however, is not determinative on whetheror not particles are suitable for injection into wood.

As used herein, particle diameters may be expressed as “d_(xx)” wherethe “xx” is the weight percent (or alternately the volume percent) ofthat component having a diameter equal to or less than the d_(xx). Thed₅₀ is the diameter where 50% by weight of the component is in particleshaving diameters equal to or lower than the d₅₀, while just under 50% ofthe weight of the component is present in particles having a diametergreater than the d₅₀. Particle diameter is preferably determined byStokes Law settling velocities of particles in a fluid, for example witha Model LA 700 or a CAPA™ 700 sold by Horiba and Co. Ltd., or aSedigraph™ 5100T manufactured by Micromeritics, Inc., which uses x-raydetection and bases calculations of size on Stoke's Law, to a size downto about 0.2 microns. Smaller sizes are preferably determined by adynamic light scattering method, preferably with a Coulter™ counter.

In one embodiment, wood or a wood product are impregnated with dispersedcopper-containing biocidal particles of the invention. Sparingly solublecopper salts in particles within wood or wood products are lessleachable than a dried injected solution of the sparingly soluble coppersalts, and is also less leachable than prior art soluble copper-aminepreservatives. Preferably, the copper-containing biocidal particles aresufficiently insoluble so as to not be quickly removed by leaching butare sufficiently soluble to exhibit toxicity to primary organismsprimarily responsible for the decay of the wood.

Generally, crystalline sparingly soluble salts are preferred becausethey have lower rates of dissolution than do amorphous salts. However,sparingly soluble amorphous salts are equally effective, andparticulates made from amorphous salts can have copper release andcopper-leach characteristics similar to those of the substantiallycrystalline sparingly soluble salts. Any discussion relating tosubstantially crystalline should be considered a preferred variant ofthe invention, as the same disclosure is generally equally applicable toamorphous sparingly soluble copper salts, or substantially amorphoussparingly soluble copper salts.

A “sparingly soluble” salt as used herein has a K_(sp) in pure waterbetween about 10⁻⁸ to about 10⁻²⁴ for salts with only one anion, andfrom about 10⁻¹² to about 10⁻²⁷ for salts with two anions. Preferredsparingly soluble salts have a K_(sp) between about 10⁻¹⁰ to about 10²¹.As used herein, preferred sparingly soluble inorganic salts includessalts with a K_(sp) of between about 10⁻¹² to about 10⁻²⁴ for salts withonly one anion, and from about 10⁻¹⁴ to about 10⁻²⁷ for salts with twoanions. Preferred sparingly soluble copper salts include copperhydroxide, basic copper carbonate, basic copper chloride (copperoxychloride), and basic copper sulfate. The copper-containingparticulates can comprise or consist essentially of any sparinglysoluble copper salts, including those selected from copper hydroxides;copper carbonates (e.g., “yellow” copper carbonate); basic (or“alkaline”) copper carbonate; basic copper phosphate, basic copperphosphosulfate, basic copper sulfates including particularly tribasiccopper sulfate; basic copper nitrates; copper oxychlorides (basic copperchlorides); copper borates; basic copper borates; Copper ferricyanate;Copper Fluorosilicate; Copper Thiocyanate; Copper diphosphate or Copperpyrophosphate, Copper Cyanate; and mixtures and combinations thereof. Ina preferred embodiment the sparingly soluble copper salts in thecopper-containing biocidal particles comprise or consist essentially ofone or more copper salts selected from copper hydroxides; coppercarbonates, basic copper carbonates; basic basic copper phosphate, basiccopper phosphosulfate, tribasic copper sulfate; copper oxychlorides(basic copper chlorides); basic copper borates, and mixtures thereof. Inone embodiment, the particles comprise at least about 20%, 30%, 50%, or75% of the weight of the any of these sparingly soluble copper salts.The most preferred inorganic copper salts are copper hydroxide and basiscopper carbonate.

In another embodiment the copper-containing particulates can comprise orconsist essentially of the group consisting of copper oxide, with theproviso that at least one of the biocides is not a copper oxide. Of thecopper oxides, Cu₂O is preferred over CuO.

In any of the above the sparingly soluble copper salt can have asubstantial amount of one or more of magnesium, zinc, or both, whereinthese cations are either dispersed within the sparingly soluble coppercomposition or be a separate phase within a particulate. In preferredembodiments of the invention, at least some particulates comprise copperhydroxide, basic copper carbonate, or both, having magnesium ionstherein. In more preferred embodiments, the copper hydroxide or basiccopper carbonate comprises between 6 and 20 parts of magnesium per 100parts of copper, for example between 9 and 15 parts of magnesium per 100parts of copper. Alternatively, in another more preferred embodiments,the copper hydroxide comprises between 6 and 20 parts total of magnesiumand zinc per 100 parts of copper, for example between 9 and 15 partstotal of magnesium and zinc per 100 parts of copper. In someembodiments, the basic copper carbonate comprises between 6 and 20 partsof magnesium per 100 parts of copper, for example between 9 and 15 partsof magnesium per 100 parts of copper, or alternatively between 6 and 20parts total of magnesium and zinc per 100 parts of copper, for examplebetween 9 and 15 parts total of magnesium and zinc per 100 parts ofcopper. Alternatively or additionally, in a preferred embodiment, thecopper hydroxide and/or basic copper carbonate comprises between about0.01 and about 5 parts of phosphate per 100 parts of copper, for examplebetween 9 and 15 parts of phosphate per 100 parts of copper.

In another preferred embodiment, slurry alternately or additionallycomprises zinc or copper borate particulates, or basic zinc borate, orbasic copper borate. As the solubility of copper borate is very pHsensitive, in a preferred embodiment the sparingly soluble copper saltscomprise an alkaline material, e.g., copper hydroxide or coppercarbonate, to reduce the solubility of the copper borate. If present,the zinc borate loading can range from 0.025% to 0.5%, for example,independent of the copper loading in the wood.

In any of the above-described embodiments, the sparingly soluble coppersalt in copper-containing particulates can further comprise thesubstantially insoluble copper salt, for example copper phosphate,Cu₃(PO₄)₂. If there are particulates substantially comprising Cu₃(PO₄)₂,copper oxide, or copper 8-quinolinolate, the particulates should beexceedingly small, e.g., less than about 0.07 microns, preferably lessthan about 0.05 microns, to provide maximum surface area to helpdissolution of the particles, and the wood treatment should contain asparingly soluble copper-salt-contining particulates, e.g., basic coppercarbonate, basic copper borate, basic copper phosphate, basic copperphosphosulfate, basic copper chloride, tribasic copper sulfate, copperhydroxides, and the like.

The zinc analogs of the above are useful for the zinc-based particulatesof the alternate embodiments of the invention. In one embodiment thecopper-based particulate material can further comprise one or moresparingly soluble zinc salts selected from zinc hydroxide; zinc oxides;zinc carbonate, basic zinc carbonate, zinc phosphate, basic zincphosphate, zinc oxychloride; zinc fluoroborate; zinc borate, zincfluoride, “basic zinc borate” (zinc borate and zinc hydroxide in closeproximity), or mixture thereof. Zinc borate, with a solubility productconstant in pure water of 5×10−11, is the preferred sparingly solublezinc salt. Further, if in the presence of a high pH, such as would beprovided by zinc hydoxide or zinc carbonate, the solubility is furtherreduced. The zinc salts may be in a separate salt phase, or may be mixedCu/Zn salts, or combinations thereof. The zinc may be in the form ofparticulate zinc oxide. In preferred embodiments the particle comprisesat least about 40%, preferably at least about 60%, and more preferablyat least about 80% by weight of one or more sparingly soluble coppersalts, sparingly soluble zinc salts, or mixtures or combinationsthereof.

In one embodiment the particulate product can comprise zinc-containingbiocidal particles comprising one or more of crystalline zinc compoundsselected from zinc hydroxide; zinc oxides; zinc carbonate; zincoxychloride; zinc fluoroborate; zinc borate, zinc fluoride, or mixturethereof. The preferred zinc-based material are zinc hydroxide, basiczinc borate, basic zinc carbonate, zinc oxide, or mixture thereof, whichmay be doped with other cations, e.g., from 0.1 to 10% copper, from 0.1to 10% magnesium, or both, for example, based on the total weight of thecations. In preferred embodiments the particle comprises at least about40%, preferably at least about 60%, and more preferably at least about80% by weight of one or more crystalline zinc compounds.

Synergy is often observed in wood preservatives with organic biocidescoupled with biocidal sparingly soluble salts, and this synergy is alsoseen in foliar applications and in non-fouling paint. It is believedthat certain organic biocides are normally long-lasting and veryeffective against most (but not all) undesired bio-organisms, but areineffective against and may be subjected to degradation be a fewbio-organisms. A principal function of the copper in such a system maybe to inhibit growth of those bio-organisms that degrade the organicbiocides and/or that are resistant to the organic biocides. The mostpreferred embodiments of this invention have copper-based particulatesand optionally one or more of zinc-based particulates and tin-basedparticulates, and further comprise between about 0.01% to about 20% byweight of one or more organic biocides, based on the weight of thecopper- and zinc-containing materials. In addition, in some embodiments,the particulates form a carrier to carry the organic biocides into thewood and help ensure the biocide is well-distributed throughout thewood. Preferred embodiments of the invention are injectablecopper-containing biocidal particles that further comprises one or moreorganic biocides attached to particulates. In other preferredembodiments, the organic biocides are themselves in injectableparticulate form, and are combined with the particulate sparinglysoluble metal salts (copper, zinc, or tin) to form an injectable slurryof particulates.

Other aspects of this invention include 1) methods to manufacture thesub-micron particulates having the narrow particle size distributionswhich are advantageous in foliar applications and antifouling paintapplications, and which are required in wood preservative applications;2) methods of formulating the compositions that comprise theparticulates for use in foliar applications, wood preservation, andpaint formulations; 3) methods of transporting the particulates; and 5)wood and wood products treated with the particulate preservativetreatment compositions. We believe the combination of methods tomanufacture injectable particles into wood, as well as our formulations,represent a significant discovery. The slurries of this invention can beessentially unaffected by the use of hard water in the slurry. Incontrast, the soluble copper-amine solutions used in the prior artprecipitated an objectionable residue of calcium and magnesiumcarbonates onto the surface of the wood. Injection of the presentformulation uses the standard operating procedure that is commonlypracticed in the industry. The present formulation reduces andoptionally eliminates the nitrogen content of the prior art products;and we believe the nitrogen is associated with the enhanced rate ofsapstain growth which presently necessitates the use of expensivesapstain control agents. Removal of the fraction of particles having adiameter greater tha 1 micron, accomplished with a component of thistechnology, also means the slurries are stable—slurry particles settleover the course of days or even weeks, so there is little danger of aslurry settling prior to injection. The sparingly soluble biocidalparticles are relatively non-leachable, being comparable with the leachrates associated with the CCA products, and being much lower than theleach rates associated with soluble copper amine wood preservatives. Dueto lower leach rates, the wood treated with the preservatives of thisinvention should be usable underground, near waterways, and also inmarine applications. The costs per pound of copper is estimated to be30% to 50% lower than present copper-MEA-carbonate preservatives.Corrosivity of the product will be less than that associated with thecopper-amine preservatives. Freight should be only one third thatassociated with the copper-amine preservatives.

DETAILED DESCRIPTION OF THE INVENTION

Unless otherwise specified, all compositions are given in “percent”,where the percent is the percent by weight based on the total weight ofthe entire component, e.g., of the particle, or to the injectablecomposition. In the event a composition is defined in “parts” of variouscomponents, this is parts by weight wherein the total number of parts inthe composition is between 90 and 110.

The term “effective” as it pertains to preservatives means the biocidalparticulates are sufficiently distributable through the wood product,and is sufficiently soluble and available so as to provide a bio-activeconcentration of copper ions in the wood matrix. By “bio-active” we meanthe preservative treatment is sufficiently biocidal to one or more offungus, mold, insects, and other undesired organisms which are normallythe target of wood preservatives such that these organisms avoid and/orcan not thrive in the treated wood. Too low a solubility (or “releaserate”), and the copper is not bioactive. At the same time, theinjectable copper-containing particles of this invention is intended tohave one or more organic-based biocides incorporated therewith inamounts the same as are currently being used with soluble copperpreservatives, and efficacy is based on the combination of the copper(and/or zinc) component in combination with the organic biocides.

By “long-lasting” we mean the preservative treatment has an effectivelife of at least about 20 years under normal outdoor ground-contact use,for example. Too high a solubility of the particulates, and the biocidesand biocidal salts are can be leached out of the wood at too fast arate. Such fast leaching creates environmental problems, i.e., theleached copper contaminates the environment, and also longevityproblems, i.e., so much biocide may be leached from the wood that theremaining treatment can no longer provide a bio-active concentration ofcopper ions.

Leaching is a function of particle size and the solubility of thesparingly soluble material. Larger size particles have lower leachrates, while particles in a size range from 1 to 10 nanometers undercertain circumstances will not have a leach rate much different thanthat of an injected and dried copper salt solution. In preferredembodiments of this invention, the d₅₀ is at least 0.04 microns, meaningat least 50% by weight of the copper-containing particulates have a sizegreater than 40 nanometers. In more preferred embodiments, the d₅₀ is0.08 microns or greater. In one preferred embodiment, at least 80% byweight of the copper-containing particulates have a size between 0.05microns and 0.4 microns.

Leaching is not the only mechanism whereby material can be flushed fromwood. Because the material is in particulate form, there is apossibility that particulates will be flushed from the wood. Evidencesuggests that very small substantially spherical nanoparticles, i.e.,spherical particles of size 5 to 20 nanometers, can migrate freelythrough a wood matrix. However, while said particles are easy to inject,they are also clearly easily transported through wood and would beeasily flushed from the wood. These wood preservative treatments wouldnot be long-lasting. Therefore, in preferred embodiments of theinvention the material is substantially free of substantially sphericalparticulates, wherein the particle diameter is less than about 20nanometers, particularly less than 15 nanometers. By substantially freewe mean the d₂₀ is greater than 0.02 microns.

Generally, the leaching rate from dispersed particulates is controlledby 1) diffusion and boundary layer effects around the limited surfacearea available to water; 2) the activation energy needed to disrupt thecrystal and to thereby cause dissolution, and 3) the absolute solubilityof the material. Solubility of copper is strongly dependent on the pH,and for the hydroxide is about 0.01 ppm at pH 10, 2 ppm at pH 7, but is640 ppm at pH 4. Wood has a “pH” between 4 and 5. Therefore, copperhydroxides are a component of the preferred substantially crystalline(or amorphous sparingly soluble) copper material, as the hydroxides willraise the pH of the water in the wood. Additionally, alkali-metal bases,such as alkali-metal hydroxides, alkali-metal carbonates, and lesspreferred alkalii-metal salts of organic carboxylic and/or sulfonic acidcontaining material having 1-4 carbon atoms per acid moiety, can beincluded in the liquid portion of the injected slurry to neutralizewood. Other useful bases include tribasic alkali phosphates and alkaliborate salts.

Leaching will be discussed extensively infra. Advantageously, theparticulates of the present invention provide at 240 hours into an AWPAE11-97 leach test a total leached copper value that is within a factorof two above, to within a factor of five below, preferably within afactor of three below, the total leached copper value obtained by a woodsample treated with CCA and subjected to the same test.

By “substantially free of hazardous material” we mean the preservativetreatment is substantially free of materials such as lead, arsenic,chromium, and the like. By substantially free of lead we mean less than0.1% by weight, preferably less than 0.01% by weight, more preferablyless than 0.001% by weight, based on the dry weight of the woodpreservative. By substantially free of arsenic we mean less than 5% byweight, preferably less than 1% by weight, more preferably less than0.1% by weight, for example less than 0.01% by weight, based on the dryweight of the wood preservative. By substantially free of chromium wemean less than 0.5% by weight, preferably less than 0.1% by weight, morepreferably less than 0.01% by weight, based on the dry weight of thewood preservative.

By “environmentally responsible” we mean the wood preservative(including co-biocide) has a bioactive effectiveness that is at leastabout equal to that of injected copper-amine preservatives. Further, theenvironmentally responsible material is substantially free of smallnanoparticles which can be readily flushed from wood. Therefore, inpreferred embodiments of the invention the d₅ is greater than 5nanometers, preferably greater than about 20 nanometers.Nanoparticle-sized metal particulates may be toxic to certain aquaticlife, though the data is very preliminary. Additionally, environmentallyresponsible wood preservatives are beneficially substantially free oforganic solvents. By substantially free we mean the treatment comprisesless than 10% organic solvents, preferably less than 5% organicsolvents, more preferably less than 1% organic solvents, for examplefree of organic solvents, based on the weight of the sparingly solubleand substantially insoluble biocides in the wood preservative.

By “injectable” we mean the wood preservative particulates are able tobe pressure-injected into wood, wood products, and the like to depthsnormally required in the industry, providing an effective dispersion ofbiocidal particles throughout the injected volume, using equipment,pressures, exposure times, and procedures that are the same or that aresubstantially similar to those currently used in industry. Pressuretreatment is a process performed in a closed cylinder that ispressurized, forcing the chemicals into the wood. Copper loading, alsocalled copper retention is a measure of the amount of preservative thatremains in the wood after the pressure is released. It is given as“pcf,” or pounds of preservative per cubic foot of wood. Retentionlevels that must be reached are dependent on three variables: the typeof wood used, the type of preservative used, and the use of the woodafter treatment. The sparingly soluble copper-salt particulates of thisinvention are typically expected to be added to wood in an amount equalto or less than 0.25 pounds as copper per cubic foot. In preferredembodiments of the invention incising is not expected to be required toinject the slurries of the present invention into lumber havingthicknesses of 6 to 10 inches.

Injectability requires the particulates be substantially free of thesize and morphology that will tend to accumulate and form a filter cake,generally on or near the surface of the wood, that results inundesirable accumulations on wood in one or more outer portions of thewood and a deficiency in an inner portion of the wood. Injectability isgenerally a function of the wood itself, as well as the particle size,particle morphology, particle concentration, and the particle sizedistribution.

Another key aspect of the invention is to make a variety of biocidalparticulate slurries available that are injectable into wood, therebyserving as a particulate wood preservative. Requirements ofinjectability into wood for substantially round, e.g., the diameter isone direction is within a factor of two of the diameter measured in adifferent direction, such as would be found in milled particles, are:

-   -   1) the d₉₆ is equal to or less than about 1 micron, but is        preferably about 0.7 microns or less, more preferably about 0.5        microns or less, for example equal to or less than about 0.3        microns, or equal to or less than about 0.2 microns;    -   2) the d₉₉ is equal to or less than about 2 microns, preferably        equal to or less than 1.5 microns, more preferably equal to or        less than about 1 micron; and    -   3), the d₅₀ is less than 0.5 microns, preferably less than 0.4        microns, and the d₅₀ is greater than 0.02 microns, more        preferably greater than 0.05 microns, for example a slurry where        the d₅₀ is between about 0.1 microns and about 0.3 microns. We        believe the first criteria primarily addresses the phenomena of        bridging and subsequent plugging of pore throats, the second        criteria addresses the phenomena of forming a filter cake, and        the third criteria addresses the issue of having particulates        disposed in the wood which have an optimum size to ensure the        treatment has an acceptable bio-activity and lifetime. Once a        pore throat is partially plugged, complete plugging and        undesired buildup generally quickly ensues.

However, there are minimum preferred particulate diameters for the woodtreatment, which depend somewhat on the copper salt(s) that are in theparticulates. If the salts have a high solubility, very smallparticulates having a large surface to mass ratio will result in toohigh a copper ion concentration, and too fast a copper leaching,compared to preferred embodiments of this invention. Generally, it ispreferred that for sparingly soluble copper or zinc salts, the d₂₀ beabove 0.01 microns in diameter, preferably greater than 0.03 microns,for example greater than 0.06 microns in diameter. While organic biocideparticles can be smaller than the sparingly soluble copper saltparticles, as these compounds generally exhibit lower solubility inwater than do the sparingly soluble copper salts, nevertheless apreferred minimum d₂₀ for organic biocide particulates is also 0.01microns.

By injectable, unless otherwise specified we mean injectable into normalsouthern pine lumber. This invention also encompasses injecting theparticulates into other woods as well as into for example heartwood.Selected other woods and heartwood may require a smaller substantiallylower criteria on particle dimensions for injectability, and suchformulations can be made as discussed herein, but the formulation mostof interest is a commercially operative formulation developed for normalSouthern Pine. Such a formulation will typically be useful for all otherwoods.

By “non-staining/non-coloring” we mean the wood preservative does notimpart undesired color to the wood. Large particulates, or largeagglomerations of smaller particulates, impose a visible and undesiredcolor to the treated wood, which for copper is generally bluish orgreenish. Surprisingly, visible coloring is usually indicative of poorinjectability or agglomeration. Individual particles of diameter lessthan about 0.5 microns that are widely dispersed in a wood matrix do notcolor a wood product to any substantial degree. Filter cake formsunsightly coloring. An aggregation of particles, similar to filter-cake,could contribute un-wanted color. Preferably the d_(99.5) is less than 1micron. Even particulates having a size greater than 0.5 microns canimpart very visible color, and agglomerates of similar size have thesame effect as do large particles. In a preferred embodiment of theinvention, the d₉₅ and more preferably the d₉₈ of the particulates andaggregates of particlates in the wood are smaller than 0.5 microns, forexample equal to or less than 0.35 microns, more preferably equal to orless than than 0.3 microns. Certain compounds, particularly basic coppercarbonate, copper hydroxide, basic copper phosphate, and copperoxychloride are preferred because they impart less color than do otherparticles of comparable size.

Additionally, the presence of a zinc salt, a magnesium salt, or botheither as a separate phase or as a mixed phase may also reduce color. Inone embodiment, fine particulates of iron oxide can be included in theinjectable slurry to help mask any visible color, and also to act as aUV blocker to protect the surface of the wood. The finely ground ironoxides are comparable to or smaller than the injectable particulatesconmprising the sparingly soluble copper or zinc salts, or the particlescomprising solid substantially insoluble organic biocide material.

By “inexpensive” we mean the wood preservative is prepared usingtechniques so that the cost of the wood treatment is competitive withfor example copper-ethanolamine-complex treatments and other commonlyused treatments. As the cost of copper is substantially constantregardless of the source, inexpensive relates primarily to the costs ofmanufacture, separation, sizing, and preservation of the particulatematerial. There are many techniques to create very small nanoparticles,but most of these processes are far too costly to be useful in the massproduction of a copper-based wood preservative treatment. Generally, theterm “inexpensive” means at a processed cost less than or equal to thecurrent costs of the soluble copper-co-biocide treatments.

The preferred method of production of the sparingly soluble copper andzinc salts begins with a precipitation process, in the absence ofwater/solvent emulsions and the like. Preferably the reactants are ofstandard industrial quality, as opposed to higher levels of purity.Feedstock of sparingly soluble salts, organic biocides, and the like canbe obtained commercially. The particles start with certaincharacteristics including size distribution and morphology, e.g., havinga d₅₀ of between 1 to 8 microns. Surprisingly, the d50 of the feedstockis relatively unimportant. The critical step in the cost-effectivemanufacturing of injectable sparingly soluble copper salt particles,injectable sparingly soluble copper oxide particles, injectablesparingly soluble zinc salt particles, injectable sparingly soluble zincoxide particles, and injectable sparingly soluble or substantiallyinsoluble organic biocide particles, is wet milling. Particles made byother processes, particularly emulsion precipitation processes andfuming processes, are not sufficiently cost effective to manufacturecommercially acceptable copper particulates for wood preservation.

Generally, the presence of any salt will induce corrosion. The woodpreservatives of the present invention have a reduced tendency, comparedto a similar concentration of copper obtained from the soluble coppertreatments such as the amine-copper-complex treatments andalkanolamine-copper-complex treatments in use today, to corrode of metalthat contacts the wood. The degree of corrosion will depend in largepart on the salts selected, as well as on adjuvants including thedispersants and stabilizers.

We also believe that another problem with the soluble amine-complexedcopper preservatives is that the commonly used soluble copper compoundsprovide nitrogen-containing nutrients (amines) which are believed to actas food-stuff and causes an increase in the presence of sapstain molds,therefore requiring additional biocides effective on sapstain molds tobe added to protect the appearance of the wood. When there is alsobio-available carbon sources, in addition to bio-available nitrogen, theproblem is made worse. Advantageously, the wood preservative issubstantially free of any amines other than certain selected amines thatmay be used as a supplemental biocide. By substantially free we mean thetreatment comprises less than 20% amines, preferably less than 10%amines, for example less than 5% amines, more preferably less than 1%amines, alternately free of amines, based on the weight of the sparinglysoluble or substantially insoluble biocides in the wood preservative.Alternatively, the term means there is less than one amine molecule ormoiety per four copper atoms, preferably less than one amine molecule ormoiety per ten copper atoms. Again, amines that are used as supplementalbiocides, if any, are excluded from this limitation. While basic coppernitrate is a useful sparingly soluble copper salt for use in thisinvention, in most embodiments of the invention the wood preservative isalso substantially free of nitrates.

Another embodiments of the invention is an injectable particulatepreservative for wood that is substantially free of bio-availablenitrogen, and also is substantially free of bio-available carbon. Bysubstantially free of bio-available nitrogen we mean the treatmentcomprises less than 10% of nitrates and organic nitrogen, preferablyless than 5% of nitrates and organic nitrogen, more preferably less than1% of nitrates and organic nitrogen, for example less than 0.1% ofnitrates and organic nitrogen, based on the weight of the copper in thewood preservative. In most of the soluble or complexed coppertreatments, there are between 1 and 4 atoms of organic nitrogen that actas a complexer or carrier for one atom of copper. In the preferredembodiments of this invention, there is less than 0.3 atoms, preferablyless than 0.1 atoms, for example less than 0.05 atoms of organicnitrogen per atom of copper in the wood preservative treatment. Again,organic nitrogen-containing compounds that are used specifically assupplemental biocides are excluded from this limitation. Bysubstantially free of bio-available carbon we mean the treatmentcomprises less than 40% of bio-available organic material (defined asmaterial that is degradable or that will during the lifespan of thetreatment will become degradable), preferably less than 20% ofbio-available organic material, more preferably less than 10% ofbio-available organic material, based on the weight of the copper in thewood preservative. Again, organic compounds that are used assupplemental biocides, if any, are excluded from this limitation. It isbelieved that the presence of bio-available organic carbon may encouragethe growth of certain molds.

In one embodiment, the copper-based particles are substantially free ofpolymers, such as organic polymers. By substantially free, it is meantthat the biocide-containing particles are less than about 50% by weightpolymer, preferably less than about 35% by weight polymer, for example,less than 25% by weight polymer, such as less than 15% by weightpolymer. In one embodiment, the copper-based particles are essentiallyfree of polymer, by which it is meant the copper-based particlescomprise less than about 5% by weight polymer. Generally, polymers, ifpresent, should be limited to the lowest practicable amount necessary toact as functional dispersants/stabilizers. The ratio of the weight ofcopper present in the particles to polymer present in the particles maybe at least about 1 to 1, for example at least about 2 to 1, 4 to 1, 5to 1, 7 to 1, or at least about 10 to 1. For example, if ratio of theweight of copper present in the particles to the weight of polymerpresent in the particles is at least about 2 to 1, the particlescomprise at least about twice as much copper by weight as polymer.

By “substantially crystalline” we mean for example greater than about30%, preferably greater than about 50%, by weight of the material ofinterest (copper salt, zinc salt, and the like) is crystalline. Amaterial is substantially crystalline if the material give thedistinctive X-ray diffraction patterns of the crystalline entity(relating to d spacing, not present in the amorphous material). Thepreferred method for determining crystallinity is by calorimetry, bymeasuring the heat of dissolution of the sample in a solvent andcomparing this heat with the measured heats of amorphous and crystallinestandard of the same salt, provided the dissolution of the crystallinesalt is substantially different than the dissolution of thecorresponding amorphous salt.

As crystallinity is difficult to measure, the following exemplarycompounds meet the requirements for substantially crystalline coppercompounds: copper(II) borate; copper boride (Cu₃B₂); yellow copper(I)carbonate; basic copper carbonate; copper(II) carbonate dihydroxide(CuCO₃×Cu(OH)₂); copper(II) carbonate dihydroxide (2CuCO₃×Cu(OH)₂);copper (I and II) chloride; copper(II) chloride×2H₂O; copper oxychloride(CuCl₂×Cu(OH)₂); copper(I and II) cyanide; copper(I and II) fluoride;copper(II) formate; copper(I and II) oxide; copper phosphate×3 water;copper(I and II) sulfate; basic copper phosphate, basic copperphosphosulfate, tribasic copper sulfate; copper silicate, and copper(I)thiocyanate. The term (I and II) means the copper(I) salt and thecopper(II) salt. These salts are further considered substantiallycrystalline with as much as 10% by weight based on the weight of thecopper being substituted with magnesium, zinc, or both. The followingexemplary compounds meet the requirements for substantially crystallinezinc compounds: zinc carbonate; zinc chloride; zinc cyanide; zincdiphosphate; zinc fluoride; zinc fluoride×4 water; zinc hydroxide; zincoxide; zinc phosphate; and zinc sulfate. These salts are further definedas substantially crystalline with as much as 10% by weight based on theweight of the zinc being substituted with magnesium, copper, or both.The following exemplary compounds meet the requirements forsubstantially crystalline tin compounds: tin(II) diphosphate(pyrophosphate); tin(II) phosphate (Sn₃(PO₄)₂); and tin(II) sulfate.

Several of the copper salts described herein are available incrystalline and in amorphous phases. Generally crystallinity ispreferred, as the lattice energy of the crystal is expected to slow downdissolution. However, amorphous copper salts are useful in theinvention, and for the less soluble salts the amorphous phases may bepreferred over crystalline phases. Phosphate-stabilized copperhydroxide, a preferred sparingly soluble copper hydroxide used inembodiments of this invention, is typically substantially amorphous.Amorphous sparingly soluble salts are equally effective, and they can betreated with one or more coatings, or can be made of a particular size,or of more insoluble salts, such that the amorphous material may easilyhave release and leach characteristics like the substantiallycrystalline salts. And discussion relating to substantially crystallineshould be considered a preferred variant of the invention, as the samedisclosure is generally equally applicable to amorphous material, orsubstantially amorphous material.

As used herein, the term “copper-containing particulate” as it pertainsto wood preservatives means a particle having a size between about 0.7microns and about 0.01 microns that comprises at least one sparinglysoluble copper salt. The term “particle” is used interchangably with theterm “particulate,” while the term “nanoparticle” refers to particleshaving a size less than about 0.01 microns in diameter. The term“copper” includes, unless specifically stated otherwise, the cuprousion, the cupric ion, or mixture thereof, or combination thereof. Theterm “copper-containing” means the particle comprises at least about20%, 30%, 50%, or 75% by weight of one or more sparingly soluble coppercompounds. In another embodiment, essentially all (e.g., more than 95%)of the weight of the copper-containing particles are composed ofsparingly soluble copper compounds.

As used herein, the term “zinc-containing particulate” as it pertains towood preservatives means a particle having a size between about 0.7microns and about 0.01 microns that comprises at least about 20%, 30%,50%, or 75% by weight of one or more substantially crystalline orsparingly soluble zinc compounds. In another embodiment, essentially all(e.g., more than 95%) of the weight of the zinc-containing particles iscomposed of one or more substantially crystalline or sparingly solublezinc compounds. The preferred sparingly soluble zinc-containingmaterials are zinc hydroxide, zinc borate (Zn(BO₂)₂×H₂O), and zinccarbonate. Again, if the borate is used as the anion, preferably thecomposition also comprises one or more salts of carbonate or hydroxideto maintain a slightly elevated pH within the wood matrix, to slowdissolution of the borate salts. If zinc-based particulates are used,they are advantageously used with copper-based particulates.

As used herein, the term “tin-containing particulate” as it pertains towood preservatives means a particle having a size between about 0.7microns and about 0.01 microns that comprises at least one sparinglysoluble tin salt. Generally, tin-based particulates are not preferredbecause tin does not have the desired bio-activity. Tin oxides arebelieved to be particularly inert. The preferred sparingly soluble tinmaterial are tin hydroxides, Sn(OH)₂ and Sn(OH)₄.

Preferred particles comprise at least 30%, preferably at least 50%, morepreferably at least 70%, for example between about 80% and about 98% byweight of total of copper hydroxides, copper(I) oxide, basic coppercarbonates, copper carbonates, copper oxychloride, basic copperphosphate, basic copper phosphosulfate, tribasic copper sulfate,alkaline copper nitrate, basic copper borate, copper silicate, ormixtures thereof. The various particles within a wood preservative cancomprise different biocides, even different sparingly soluble coppersalts. For example, a treatment may contain particles that comprisecopper borate or copper borate in combination with copper hydroxideand/or basic copper salt, particularly basic copper carbonate, otherparticles that comprise basic copper carbonate, optionally patrticlesthat comprise basic copper phosphate, and even other particles thatcomprise copper oxide. The particles having different phases may inpreferred embodiments be of different sizes, depending on the coppermaterial present.

In one embodiment, exemplary wood preservatives have a d₅₀ equal to orsmaller than 0.5 μm, 0.25 μm, 0.2 μm, or 0.15 μm. Advantageously, thed₉₆, and preferably the d₉₉, are within a factor of three of the d₅₀,and very preferably is less than 1.2 microns. In one embodiment, the d₅₀is at least 25 nanometers, for example, at least 50 nanometers.

There is a large number of references describing how to makecopper-containing “nanoparticles.” These references generally can not beused to manufacture the particulates at the desired cost. One methodthat is particularly not cost effective is using an emulsionprecipitation or emulsion crystallization technique, where smallparticles are allowed to grow in a certain phase of an emulsion, wherethe ultimate size of the particle is limited by the amount of acomponent in a droplet in the emulsion. Both inorganic salts and organicbiocidal particulates can be formed in this manner, but not at a costwhere such materials would be useful for foliar applications on cropsnor for wood preservation.

In one embodiment of the invention, a preliminary copper-based particlesare prepared, such as by precipitation, from a mixture comprising copperand an amine. The copper and amine may be present in the form of acopper-amine complex. Preferred precipitates comprise copper hydroxides.The particles may be prepared by modifying a pH of the mixturecomprising copper and the amine, surprisingly in a downward direction topH 6 or with an alkali hydroxide to obtain a pH greater than about 13. Adispersant may be added to the mixture before obtaining the precipitate.In one embodiment, the pH is adjusted so that the pH is between about5.5 to about 7. Suitable acids for adjusting the pH include, forexample, sulfuric acid, nitric acid, hydrochloric acid, formic acid,boric acid, acetic acid, carbonic acid, sulfamic acid, phosphoric acid,phosphorous acid, and/or propionic acid. The anion of the acid used maybe partially incorporated in the precipitated salt, as may othercations, such as magnesium and/or zinc.

Another embodiment of a method for preparing copper-based particlescomprises precipitation of copper-based particles from a solutioncomprising (a) copper, such as in the form of a copper salt, and (b) apH modifying agent, such as a hydroxide. Exemplary hydroxides may beselected from hydroxides of group 1a and/or group 2a elements, such assodium and potassium hydroxide.

U.S. Pat. No. 4,808,406, the disclosure of which is incorporated byreference, describes a useful method for producing finely divided stablecupric hydroxide composition of low bulk density comprising contactingsolutions of an alkali metal carbonate or bicarbonate and a copper salt,precipitating a basic copper carbonate-basic copper sulfate to a minimumpH in the range of greater than 5 to about 6, contacting the precipitatewith an alkali metal hydroxide and converting basic copper sulfate tocupric hydroxide. Another method of manufacturing the copper compoundsis the method described in U.S. Pat. No. 4,404,169, the disclosure ofwhich is incorporated by reference. This patent describes a process ofproducing cupric hydroxides having stability in storage if phosphateions are added to a suspension of copper oxychloride in an aqueousphase. The copper oxychloride is then reacted with alkali metalhydroxide or alkaline earth metal hydroxide, and the cupric hydroxideprecipitated as a result of the suspension is washed and thenre-suspended and subsequently stabilized by the addition of acidphosphate to adjust a pH value of 7.5 to 9. The suspended copperoxychloride is preferably reacted in the presence of phosphate ions inan amount of 1 to 4 grams per liter of the suspension and at atemperature of 20° to 25° C. and the resulting cupric hydroxide isstabilized with phosphate ions.

There are numerous methods of preparing very small particles of coppersalts, and the above list is exemplary and not complete. It is importantto note that the size of the precipitates is relatively unimportant,annd the cost of the reagents is exceedingly important. The materialneed not be of high purity. Indeed, it is desirable to have one or more“contaminants” in the precipitating solutions. Smaller diameters areobtained when the concentration of impurities such as Mg, Ca, Zn, Na, Aland Fe in the suspension is high. Fe present in the suspension actsespecially strongly to prevent formation of large-diameter cuproushydroxide particles.

Copper hydroxide is not particularly stable. Hydroxides can be changedto oxides by for example in a quick and exothermic reaction by exposureof the copper hydroxide particles to aqueous solution of glucose. Copperhydroxide may react with air, sugars, or other compounds to partially orcompletely form copper oxide. The conditions for conversion are highlyfavored during kiln-drying treated wood, which contains gluconuuronicacids, which are sugar-like molecules, and heat and a dehydratingcondition. However, as taught by U.S. Pat. No. 3,231,464, the disclosureof which is incorporated herein by reference thereto, the presence ofmagnesium or magnesium and zinc can help stabilize cupric hydroxide fromconverting to copper oxide via the loss of a water molecule. Thepreferred copper hydroxide particles used in this invention arestabilized. U.S. Pat. No. 3,231,464 teaches stabilizing the copperhydroxide with added magnesium zinc, or both, at a Cu:Mg and/or Cu:Znweight ratio of 8:1. Copper hydroxide prepared in a manner so as tocontain significant magnesium and/or zinc hydroxides are more stable andresistant to degradation to copper oxides. The preferred copperhydroxide particles comprise between 50% and 90 copper hydroxide, withthe remainder comprising zinc hydroxide, magnesium hydroxide, or both.

In one embodiment of the invention, copper-based particles areprecipitated from a mixture of a copper salt solution and a hydroxide(and optionally other anions) in the presence of at least one group 2ametal or salt thereof, such as magnesium or a magnesium salt. In oneembodiment, the copper-based particles are precipitated from a mixturecomprising at least about 0.05 parts magnesium, for example at leastabout 0.1 parts magnesium per 9 parts copper. The mixture may compriseat least about 0.25 parts magnesium per 9 parts copper. The mixture maycomprise less than about 1.5 parts magnesium, for example, less thanabout 1.0 parts, or less than about 0.75 parts magnesium per 9 partscopper. Copper-based particles prepared in accordance with the presentinvention will comprise a group 2a metal or zinc if such materials(metal ions) were used in preparation of the particles. In anotherembodiment, the copper-based particles are precipitated from a mixturecomprising at least about 0.2 parts magnesium, for example at leastabout 0.25 parts magnesium per 22.5 parts copper. The mixture maycomprise at least about 0.5 parts magnesium per 22.5 parts copper. Themixture may comprise less than about 3.5 parts magnesium, for example,less than about 2.5 parts magnesium, or less than about 2 partsmagnesium per 22.5 parts copper. The parts here merely reflect weightratios of the cations in the solution to be precipitated, and the partsdo not imply concentration.

Alternatively, or in combination with the group 2a metal or saltthereof, the copper-based particles may be precipitated from a solutioncomprising zinc metal or salt thereof. For example, the mixture maycomprise at least about 0.1 parts zinc, for example, at least about 0.25parts zinc, at least about 1.0 parts zinc, or at least about 2.0 partszinc per 22.5 parts copper. The mixture may comprise less than about 3.0parts zinc, for example, less than about 2.5 parts zinc, or less thanabout 1.5 parts zinc per 22.5 parts copper. Preferably, the mixtureadditionally comprises at least about 0.25 parts magnesium, for example,at least about 0.5 parts magnesium, at least about 1.0 parts magnesium,or at least about 2 parts magnesium per 22.5 parts copper. The mixturemay comprise less than about 5.0 parts magnesium, for example, less thanabout 2.5 parts magnesium, or less than about 2 parts magnesium per 22.5parts copper.

While svarious precipitation methods can provide small particles ofsparingly soluble salts, the product usually has a small fraction ofparticles that are unacceptably large. A very small fraction ofparticles having a particle size above about 1 micron causes, ininjection tests on wood specimens, severely impaired injectability.Large particles, e.g., greater than about 1 micron in diameter, shouldbe broken down by wet-milling. Even for processes that provide verysmall median diameter particles, say a few tenths of a micron indiameter, the precipitation process seems to result in a small fractionof particles that are larger than about 1 micron, and these particlesplug up pores and prevent acceptable injectability. The d₉₉, preferablythe d_(99.5), of injectable particles is less than about 1 micron.Additionally, wet milling preferentially breaks down rod-shapedparticles, which are particularly troublesome.

We have surprisingly found that wet ball milling, with milling media ofspecified characteristics, can advantageously modify particle size andmorphology of sparingly soluble copper salts, sparingly soluble zincsalts, copper oxides, zinc oxides, iron oxides, and even solid organicbiocides known to be highly resistant to milling, such aschlorothalonil, to a size wher the compounds are readily injectable intowood. This finding is central to the invention. We have surprisinglyfound that both organic and inorganic particulates can be readily milledinto an injectable material by wet milling with a milling material suchas a 0.3 to a 0.7 mm milling media having density greater than 3grams/cm³, for example equal to or greater than 3.8 grams/cm³ such as0.5 mm diameter zirconium silicate, preferably greater than 5.5,grams/cm³ provided by a 0.5 mm milling bead of zirconium oxide which maycontain one or more dopants such as cerium and/or yttrium, and/ormagnesia in a stabilizing amount. Additionally, regardless of theparticle size of the feedstock, the particles can be broken down toinjectable size in a matter of minutes to at most a few hours.Beneficially all injectable formulations for wood treatment should bewet-milled, even when the “mean particle size” is well within the rangeconsidered to be “injectable” into wood.

The milling media, also called grinding media or milling beads, iscentral to this invention. The selection of milling media is expresslynot a routine optimization. The use of this media allows an averageparticle size and a narrow particle size distribution that hadpreviously not been obtainable in the art, nor did the results in theprior art allow one to predict the unexpected results we obtained. Amajor contribution of this invention is a method of preparing aparticulate biocide product having a d₅₀ equal to or less than about 1micron, comprising the steps of: 1) providing the solid inorganic ororganic biocide, and a liquid comprising a surface active agent, to amill; providing a milling media comprising an effective amount ofmilling beads having a diameter between 0.1 mm and 0.8 mm, preferablybetween about 0.2 mm and about 0.7 mm, more preferably between about 0.3mm and about 0.6 mm, wherein these milling beads have a density greaterthan about 3 grams/cm3, preferably equal to or greater than 3.5grams/cm3, more preferably equal to or greater than 3.8 grams/cm3, mostpreferably equal to or greater than 5.5 grams/cm3, for example azirconia bead having a density of about 6 grams/cm3; and 2) wet millingthe material at high speed, for example between 300 and 6000 rpm, morepreferably between 1000 and 4000 rpm, for example between about 2000 and3600 rpm, where milling speed is provided for a laboratory scale ballmill, for a time sufficient to obtain a product having a mean volumeparticle diameter of about 1 micron or smaller, for example betweenabout 5 minutes and 300 minutes, preferably from about 10 minutes toabout 240 minutes, and most preferably from about 15 minutes to about 60minutes. As little as 5% by volume of the milling media need be withinthe preferred specifications for milling some materials, but betterresults are obtained if greater than 10% by weight, preferably greaterthan 25% by weight, for example between 40% and 100% by weight of themilling material is within the preferred specifications. For millingmaterial outside the preferred specifications, advantageously thismaterial has a density greater than 3 grams/cm³ and a diameter less than4 mm, for example 1 or 2 mm zirconia or zircionium silicate millingbeads.

The milling media advantageously comprises or consists essentially of azirconium-based material. The preferred media is zirconia (density ˜6g/cm³), which includes preferred variants such as yttria stabilizedtetragonal zirconium oxide, magnesia stabilized zirconium oxide, andcerium doped zirconium oxide. For some biocides, zirconium silicate(density ˜3.8 g/cm³) is useful. However, for several biocides such aschlorothalanil, zirconium silicate will not achieve the required actionneeded to obtain the narrow sub-micron range of particle sizes inseveral preferred embodiments of this invention. In an alternateembodiment, at least a portion of the milling media comprises orconsists essentially of metallic material, e.g., steel. The millingmedium is a material having a density greater than about 3.5, preferablyat least about 3.8, more preferably greater than about 5.5, for exampleat least about 6 g/cm³.

We believe that density and particle size are the two most importantparameters in the milling media. Preferably the milling media comprisesor consists essentially of particles, having a size (diameter) betweenabout 0.1 mm and about 0.8 mm, preferably between about 0.3 mm and about0.7 mm, for example between about 0.4 mm and 0.6 mm. Also preferably,the milling media can have a density greater than about 3.8 g/cm³,preferably greater than about 5.5 g/cm³, more preferably greater thanabout 6 g/cm³. The zirconium-based milling media useful in the presentinvention can comprise or consist essentially of particles having adiameter (as the term is used in the art) between about 0.1 mm and about0.8 mm, preferably between about 0.3 mm and about 0.7 mm, for examplebetween about 0.4 mm and 0.6 mm.

Not all the milling media need be the preferred material, e.g., having apreferred diameter between 0.1 mm and 0.8 mm, preferably between 0.2 mmand 0.7 mm, more preferably between 0.3 mm and 0.6 mm, and having apreferred density equal to or greater than 3.8 grams/cm³, preferablygreater than or equal to 5.5 grams/cm³, more preferably greater than orequal to 6 grams/cm³. In fact, as little as 10% of this media willprovide the effective grinding. The amount of the preferred millingmedia, based on the total weight of media in the mill, can be between 5%and 100%, is advantageously between 10% and 100%, and is preferablybetween 25% and 90%, for example between about 40% and 80%. Media notwithin the preferred cattegory can be somewhat larger, say 1 mm to 4 mmin diameter, preferably from 1 mm to 2 mm in diameter, andadvantageously also has a density equal to or greater than 3.8grams/cm³.

A first aspect of the invention is a method of preparing a submicronbiocide product comprising the steps of: 1) providing the solid biocidein particle form to a ball mill, providing a liquid to a mill, andproviding a milling media to the mill, wherein the milling mediacomprises at least 5%, preferably at least 10%, more preferably at least25% by weight of the milling media having a particle diameter between0.1 to 0.8 mm, preferably between 0.3 and 0.7 mm, and having a densityequal to or greater than 3.8 g/cm³, preferably equal to or greater than5.5 g/cm³; and 2) milling the material for a time sufficient to obtain aproduct having a mean volume particle diameter d₅₀ of about 1 micron orsmaller. The mill speed is advantageously fast, for example from 1000rpm to about 4000 rpm, and the milling time is preferably between 10minutes and 240 minutes.

Generally, less dense milling media will provide a relatively largerd₅₀, which can be useful for foliar applications. The denser millingmedia, for example media having a density greater than 5.5 g/cm³,provides a smaller d₅₀. Surprisingly, varying the milling time has verylittle affect on the d₅₀. The preferred dense milling media iszircionia, cerium doped zirconia. The zirconium oxide can comprise anystabilizers and/or dopants known in the art, including, for example,cerium, yttrium, and magnesium. An alternate useful dense millingmaterial is steel. Generally, at least 25% by weight of the millingmedia must have a density greater than 3.8 and a diameter between 0.1and 0.7 mm to reliably obtain injectable particles of sparingly solublecopper salts.

Manufacturing injectable solid substantially insoluble organic biocideparticles, e.g., chlorothalonil, can beneficially be performed by 1)providing the chlorothalonil and a liquid comprising surface activeagents to a mill, and 2) milling the material with a milling mediahaving a density greater than 5.5 grams/cm³, for example milling beadscomprising a zirconium oxide having a diameter between about 0.1 mm andabout 0.7 mm. The invention also encompasses a organic biocideparticulate product, e.g., a chlorothalonil product, having a d₅₀ belowabout 1 micron, typically below about 0.5 microns, and preferablybetween 0.1 and 0.3 microns, which advantageously also exhibits a d₉₀that is less than about three times the d₅₀, preferably less than abouttwo times the d₅₀.

The attainment of the injectable size, which generally requires both ad₅₀ below 0.5 microns and a d₉₈ less than three times the d₅₀, was asurprising development. Milling sparingly soluble copper salts forseveral days with a 2 mm milling media could not provide the requiredparticle size distribution, even if the feed material had a d50 of lessthan 0.3 microns. Milling a milling-resistant organic biocide with 1 mmzirconia provided a chlorothalonil product with a d₅₀ of 2 to 3 microns.Yet, surprisingly, milling each of these with a preferred milling media,e.g., zirconia-based milling beads having a diameter between 0.4 and 0.5mm, provided each of these products in injectable sub-micron slurries inunder a few hours, often in less than 30 minutes.

Advantageously, the liquid comprises one or more dispersants and/orstabilizers. The presence of these promotes a smaller d50 and a narrowerparticle size distribution, because agglomeration of particulates isdiscouraged. Aqueous dispersing agents for such dispersed solids arewell known to those skilled in the art and include, but are not limitedto, nonionic surfactants such as ethylene oxide/propylene oxide blockcopolymers, polyvinyl alcohol/polyvinyl acetate copolymers, polymericnonionic surfactants such as the acrylic graft copolymers; anionicsurfactants such as polyacrylates, lignosulfonates, polystyrenesulfonates, maleic anhydride-methyl vinyl ether copolymers, naphthalenesulfonic acid formaldehyde condensates, phosphate ester surfactants suchas a tristyrenated phenol ethoxylate phosphate ester, maleicanhydride-diisobutylene copolymers, anionically modified polyvinylalcohol/polyvinylacetate copolymers, and ether sulfate surfactantsderived from the corresponding alkoxylated nonionic surfactants;cationic surfactants; zwitterionic surfactants; and the like.

The milling of the organic biocides is advantageously performed in thepresence of an aqueous medium containing surfactants and/or dispersants,such as those known in the art. Use of other media, including forexample polar organic solvents such as alcohols, generally does notoffer added advantage sufficient to outweigh the cost and associatedhazards of milling with solvents. Because it is now possible to achievea smaller particle size and a narrower particle size distribution usingthe present invention than was previously known in the art, the numberand amount of stabilizers and/or dispersants are less critical. As usedherein, the term “surface active agent” includes both singlular andplural forms and encompasses generally both stabilizers and dispersants.The surface active agent may be anionic, cationic, zwitterionic, ornonionic, or a combination thereof. Generally, higher concentrations ofsurface active agents present during milling result in a smallerparticle size.

However, because we have surprisingly found a milling media andconditions where very small particles and a narrow particle sizedistribution are obtainable, we can use less/lower amounts ofstabilizers and/or dispersants than would otherwise be used. Forexample, advantageously the total weight of surface active agents in thepresent invention can be less than about 1.5 times the weight of theparticulate organic biocide, preferably less than about the weight ofthe particulate organic biocide. A stabilizing amount of the surfaceactive agent can be used, generally not less than about 2%, andtypically not more than about 60% by weight, based on the weight of theparticulate organic biocide. Other adjuvants, such as: fillers includingbiocidal fillers such as zinc oxide and non-biocidal fillers such assilica; stabilizer/dispersants such as a poly(oxypropylene) blockcopolymer with poly(oxyethylene), commercially available from BASF,PROXEL GXL (1,2-benzisothiazolin-3-one, commercially available from ICI,and/or PVP K-30 poly(vinyl pyrrolidone), commercially available fromBAS; typical viscosity modifiers/stabilizers such as xanthan gumcommercially available from Kelco); typical anti-foaming agents such asAntifoam FG-10, a silicon emulsion commercially available from DowCorning; antifreeze such as propylene glycol; chelators such as EDTA,HEDP, and the like, can be added to the water before or during milling.Milling is best done in a wet mill or high speed media mill.

Examples of suitable classes of surface active agents include, but arenot limited to, anionics such as alkali metal fatty acid salts,including alkali metal oleates and stearates; alkali metal laurylsulfates; alkali metal salts of diisooctyl sulfosuccinate; alkyl arylsulfates or sulfonates, lignosulfonates, alkali metal alkylbenzenesulfonates such as dodecylbenzene sulfonate, alkali metal soaps,oil-soluble (e.g., calcium, ammonium, etc.) salts of alkyl aryl sulfonicacids, oil soluble salts of sulfated polyglycol ethers, salts of theethers of sulfosuccinic acid, and half esters thereof with nonionicsurfactants and appropriate salts of phosphated polyglycol ethers;cationics such as long chain alkyl quaternary ammonium surfactantsincluding cetyl trimethyl ammonium bromide, as well as fatty amines;nonionics such as ethoxylated derivatives of fatty alcohols, alkylphenols, polyalkylene glycol ethers and condensation products of alkylphenols, amines, fatty acids, fatty esters, mono-, di-, ortriglycerides, various block copolymeric surfactants derived fromalkylene oxides such as ethylene oxide/propylene oxide (e.g., PLURONIC™,which is a class of nonionic PEO-PPO co-polymer surfactant commerciallyavailable from BASF), aliphatic amines or fatty acids with ethyleneoxides and/or propylene oxides such as the ethoxylated alkyl phenols orethoxylated aryl or polyaryl phenols, carboxylic esters solubilized witha polyol or polyvinyl alcohol/polyvinyl acetate copolymers, polyvinylalcohol, polyvinyl pyrrolidinones (including those sold under thetradenames AGRIMER™ and GANEX™), cellulose derivatives such ashydroxymethyl cellulose (including those commercially available from DowChemical Company as METHOCEL™), and acrylic acid graft copolymers;zwitterionics; and the like; and mixtures, reaction products, and/orcopolymers thereof.

Additionally or alternatively, the surface active agent may include, butis not limited to, low molecular weight sodium lauryl sulfates, calciumdodecyl benzene sulfonates, tristyryl ethoxylated phosphoric acid orsalts, methyl vinyl ether-maleic acid half-ester (at least partiallyneutralized), beeswax, water soluble polyacrylates with at least 10%acrylic acids/salts, or the like, or a combination thereof.

Additionally or alternatively, the surface active agent may include, butis not limited to, alkyl grafted PVP copolymers commercially availableas GANEX™ and/or the AGRIMER™ AL or WP series, PVP-vinyl acetatecopolymers commercially available as the AGRIMER™ VA series, ligninsulfonate commercially available as REAX 85A (e.g., with a molecularweight of about 10,000), tristyryl phenyl ethoxylated phosphoricacid/salt commercially available as SOPROPHOR™ 3D33, GEROPON™ SS 075,calcium dodecylbenzene sulfonate commercially available as NINATE™ 401A, IGEPAL™ CO 630, other oligomeric/polymeric sulfonated surfactantssuch as Polyfon H (molecular weight ˜4300, sulfonation index ˜0.7, saltcontent ˜4%), Polyfon T (molecular weight ˜2900, sulfonation index ˜2.0,salt content ˜8.6%), Polyfon O (molecular weight ˜2400, sulfonationindex ˜1.2, salt content ˜5%), Polyfon F (molecular weight ˜2900,sulfonation index ˜3.3, salt content ˜12.7%), Reax 88B (molecular weight˜3100, sulfonation index ˜2.9, salt content ˜8.6%), Reax 100 M(molecular weight ˜2000, sulfonation index 3.4, salt content ˜6.5%), andReax 825 E (molecular weight ˜3700, sulfonation index ˜3.4, salt content˜5.4%), and the like.

Other notable surface active agents can include nonionic polyalkyleneglycol alkyd compounds prepared by reaction of polyalkylene glycolsand/or polyols with (poly)carboxylic acids or anhydrides; A-B-Ablock-type surfactants such as those produced from the esterification ofpoly(12-hydroxystearic acid) with polyalkylene glycols; high molecularweight esters of natural vegetable oils such as the alkyl esters ofoleic acid and polyesters of polyfunctional alcohols; a high molecularweight (MW>2000) salt of a naphthalene sulfonic acid formaldehydecondensate, such as GALORYL™ DT 120L available from Nufarm; MORWET EFW™available from Akzo Nobel; various Agrimer™ dispersants available fromInternational Specialties Inc.; and a nonionic PEO-PPO-PEO triblockco-polymer surfactant commercially available as PLURONIC™ from BASF.

Other examples of commercially available surface active agents includeAtlox 4991 and 4913 surfactants (Uniqema), Morwet D425 surfactant(Witco), Pluronic P105 surfactant (BASF), Iconol TDA-6 surfactant(BASF), Kraftsperse 25M surfactant (Westvaco), Nipol 2782 surfactant(Stepan), Soprophor FL surfactant (Rhone-Poulenc), Empicol LX 28surfactant (Albright & Wilson), Pluronic F108 (BASF).

In one embodiment, exemplary suitable stabilizing components includepolymers or oligomers having a molecular weight from about 250 to about10⁶, preferably from about 400 to about 10⁵, more preferably from about400 to about 10⁴, and can include, for example, homopolymers orco-polymers described in “Polymer Handbook,” 3rd Edition, edited by J.Brandrup and E. H. Immergut.

In another embodiment, exemplary suitable stabilizing components includepolyolefins such as polyallene, polybutadiene, polyisoprene,poly(substituted butadienes) such as poly(2-t-1 butyl-1,3-butadiene),poly(2-chlorobutadiene), poly(2-chloromethyl butadiene),polyphenylacetylene, polyethylene, chlorinated polyethylene,polypropylene, polybutene, polyisobutene, polybutylene oxides,copolymers of polybutylene oxides with propylene oxide or ethyleneoxide, polycyclopentylethylene, polycyclolhexylethylene, polyacrylatesincluding polyalkylacrylates and polyarylacrylates, polymethacrylatesincluding polyalkylmethacrylates and polyarylmethacrylates,polydisubstituted esters such as poly(di-n-butylitaconate),poly(amylfumarate), polyvinylethers such as poly(butoxyethylene) andpoly(benzyloxyethylene), poly(methyl isopropenyl ketone), polyvinylchloride, polyvinyl acetate, polyvinyl carboxylate esters such aspolyvinyl propionate, polyvinyl butyrate, polyvinyl caprylate, polyvinyllaurate, polyvinyl stearate, polyvinyl benzoate, polystyrene,poly-t-butyl styrene, poly (substituted styrene), poly(biphenylethylene), poly(1,3-cyclohexadiene), polycyclopentadiene,polyoxypropylene, polyoxytetramethylene, polycarbonates such aspoly(oxycarbonyloxyhexamethylene), polysiloxanes, in particular,polydimethyl cyclosiloxanes and organo-soluble substituted polydimethylsiloxanes such as alkyl, alkoxy, or ester substitutedpolydimethylsiloxanes, liquid polysulfides, natural rubber andhydrochlorinated rubber, ethyl-, butyl- and benzyl-celluloses, celluloseesters such as cellulose tributyrate, cellulose tricaprylate, andcellulose tristearate, natural resins such as colophony, copal, andshellac, and the like, and combinations or copolymers thereof.

In still another embodiment, exemplary suitable stabilizing componentsinclude co-polymers of styrene, alkyl styrenes, isoprene, butenes,butadiene, acrylonitrile, alkyl acrylates, alkyl methacrylates, vinylchloride, vinylidene chloride, vinyl esters of lower carboxylic acids,and α,β-ethylenically unsaturated carboxylic acids and esters thereof,including co-polymers containing three or more different monomer speciestherein, as well as combinations and copolymers thereof.

In yet another embodiment, exemplary suitable stabilizing componentsinclude polystyrenes, polybutenes, for example polyisobutenes,polybutadienes, polypropylene glycol, methyl oleate,polyalkyl(meth)acrylate e.g. polyisobutylacrylate orpolyoctadecylmethacrylate, polyvinylesters e.g. polyvinylstearate,polystyrene/ethyl hexylacrylate copolymer, and polyvinylchloride,polydimethyl cyclosiloxanes, organic soluble substituted polydimethylsiloxanes such as alkyl, alkoxy or ester substitutedpolydimethylsiloxanes, and polybutylene oxides or copolymers ofpolybutylene oxides with propylene and/or ethylene oxide. In oneembodiment, the surface active agent can be adsorbed onto the surface ofthe biocide particle, e.g., in accordance with U.S. Pat. No. 5,145,684.

Another aspect of the invention is a method of preparing a submicronorganic biocide product for use as a foliar treatment, or as an additivein paints or coatings, comprising the steps of: 1) providing the organicbiocide to a mill, and 2) milling the material with a milling mediahaving a density greater than about 3.5 and having a diameter betweenabout 0.1 mm and about 0.7 mm. The density of the milling media, andespecially of the milling media within the size range 0.3 to 0.7 mm, isadvantageously greater than about 3.8, for example greater than about 4,preferably greater than about 5.5, for example equal to or greater thanabout 6 grams per cubic centimeter. Ceramic milling media is preferredover metallic milling media.

In each embodiment, the milling load is preferably about 50% of thevolume of the mill, though loadings between 40% and 80% are efficient.In each embodiment, advantageously water and surface active agents areadded to the product before or during milling. In each embodiment, theproduct can be transported as a stable slurry, as a wettable powder, oras granules that disintegrate on mixing with water to release theproduct.

Wet milling can be done in a sand grinder charged with for examplepartially stabilized zirconia beads with diameter 0.5 mm; alternatelywet milling in a rotary sand grinder with partially stabilized zirconiabeads with diameter 0.5 mm and with stirring at for example 1000 rpm; orby use of a wet-ball mill, an attritor (e.g., manufactured by MitsuiMining Ltd.), a perl mill (e.g., manufactured by Ashizawa Ltd.,), or thelike. Modifications of the above processes are within the skill of oneof ordinary skill in the art, and such modifications will not bedescribed here.

However, we surprisingly found that a milling process using 0.5 mm highdensity zirconium silicate and more preferably 0.5 mm zirconia grindingmedia provides further efficient attrition, especially for the removalof particles greater than about 1 micron in the commercially availablecopper-based particulate product available from Phibro-Tech., Inc. Themilling process usually takes on the order of minutes to achieve almostcomplete removal of particles greater than 1 micron in size. This wetmilling process is inexpensive, and all of the precipitate can be usedin the injectable copper-containing particulate wood treatment. Themilling agents can be zirconia, partially stabilized zirconia, zirconiumsilicate, and yttrium/zirconium oxide, for example, recognizing that themore dense materials give faster particle size attrition. The size anddensity of the milling material is believed to be important, evencritical, to obtaining a commercially acceptable process. The millingagent material having a diameter of 2 mm or greater are ineffective overhours and days, milling material of diameter of 1 mm is ineffective overtimes in the prior art, e.g., 10 minutes to an hour, while milling agentmaterial having a diameter of 0.5 mm is effective typically after 15minutes of milling.

We have surprisingly found that copper-based particulates that aremanufactured by a straightforward precipitation process, usingconditions known in the art to produce small particles, e.g., particleshaving a size less than 10 microns, can be readily milled into aninjectable material. Therefore, milling other precipitate material with0.5 mm diameter zirconium silicate (or any comparable product, e.g., a0.3 mm to 0.7 mm sized zirconium silicate or zirconium oxide) can millin a matter of minutes a substantially crystalline (or amorphoussparingly soluble) powder material having a larger initial average sizeinto a product that can be readily injected into wood. Milling with 0.5mm zirconium silicate and/or zirconia media not only quickly reducedfurther the magnesium stabilized copper hydroxide product, but thisgrinding medium was also found to be effective of other forms of basiccopper compounds such as other stabilized copper hydroxides, coppercarbonate, tribasic copper sulfate, copper oxychloride, and copperoxides, and also on solid organic biocides. The results of milling of avariety of materials with the 0.5 mm milling material described abovefor 15 minutes are shown in Table 2. Copper hydroxide material with aninitial median size of 2.5 microns was quickly milled to an injectablematerial having a median particle size of 0.3 microns. Additionalmilling time would doubtless further reduce the median and averageparticle size. A copper carbonate material having a median size of 3.4microns was milled to a material having a median size of less than 0.2microns. FIG. 1 shows the face of wood injected with unmilled productand the face of wood injected with the milled product. In the colorphotographs the plugging is especially visible. A tribasic coppersulfate material having a median size of 6.2 microns was milled to amaterial having a median size of less than 0.2 microns in under 30minutes. A copper oxychloride material having a median size of 3.3microns was milled to a material having a median size of 0.4 microns.

Milling is believed to break up larger particles. It would also breakparticles having one large dimension, e.g., rod-like particles, whichare know to have injection problems. Milling can be combined with forexample centrifugation to create a more uniform product. Alternatively,milling can be combined with a coating process to form a more stablematerial.

In another preferred embodiment, slurry comprises a sparingly solublecopper salt particulates and also comprises zinc borate particulates.Preferably at least some of the sparingly soluble copper salt-basedparticulates comprise copper borate. It is known to use a two stageprocess where a zinc or copper salt is injected into the wood followedby a second step wherein the borax is injected and the insoluble metalborate is formed in situ. Such a complicated, time-consuming, andtherefore expensive process in not sufficiently cost-effective. As thesolubility of copper borate is very pH sensitive, in a preferredembodiment the sparingly soluble copper salts comprise an alkalinematerial, e.g., copper hydroxide or copper carbonate, to reduce thesolubility of the copper borate.

In any of the above-described embodiments, the preservative can furthercomprise the substantially insoluble copper salt copper phosphate,Cu₃(PO₄)₂. Generally, in preferred embodiments, if Cu₃(PO₄)₂ is presentit is a coating over other sparingly soluble copper salts, wherein theCu₃(PO₄)₂ provides a fairly inert coating for a period of time before itdissolves or partially dissolves.

In any of the above-described embodiments, the preservative can furthercomprise the substantially insoluble copper salt copper phosphate,Cu₃(PO₄)₂. If there are copper-based-particulates substantiallycomprising CU₃(PO₄)₂ and/or copper oxide, the particulates should beexceedingly small, e.g., less than about 0.05 microns, preferably lessthan about 0.04 microns, to provide maximum surface area to helpdissolution of the particles, and the wood treatment should containanother type of substantially crystalline (or amorphous sparinglysoluble) copper-based particulates, e.g., basic copper carbonate, copperborate, tribasic copper sulfate, copper hydroxides, and the like.

Basic copper phosphate is more preferred for the solid particulates, asit is more soluble and more bioactive than copper phosphate.Additionally, the phosphate ions can retard leaching of copper,neutralize acids in the wood, and in some instances help reducecorrosivity of the treated wood to metals. Mixtures of basic copperphosphate and basic copper sulfate are also useful, and they are oftencalled basic copper phosphosulfate.

Conversely but advantageously, basic copper borate has a lowersolubility than copper borate, which is advantageous because copperborate particles can dissolve fairly quickly, in terms of the expectedlife of a wood preservative. Basic copper borate has an advantage thatthe anion, borate, has advantageous biocidal and fire retardingproperties.

As copper salts are millable and injectable, and organic biocides thatare known to be difficult to mill are millable and injectable, there isno reason to doubt that organo-copper compiounds will also not bemillable and injectable. In any of the embodiments, the preservative maycomprise copper organic materials, especially those materials having asparingly soluble partially crystalline nature, e.g., the ground copperorganic salts disclosed in U.S. Pat. No. 4,075,326. In any of theabove-described embodiments, the copper composition in copper-basedparticulates and/or copper-based particulate material can furthercomprise the substantially insoluble copper salt copper 8-quinolinolate.In any of the above-described embodiments, the composition can furthercomprise copper quinaldate, copper oxime, or both in particulate form.Its particularly noteworthy that organo-metallic meterials, such as thecopper salt of 8-hydroxyquinoline, copper oxime, and even traditionallyoil-borne biocides such as copper naphthaenate, can now be milled intosubmicon injectable particles, and injected into and dispersedthroughout wood, without use of dissolving oils. The zinc analogs areequally millable.

Preferred embodiments of the invention comprise particles comprising oneor more of copper hydroxide, alkaline copper carbonate, alkaline copperoxychloride, tribasic copper sulfate, alkaline copper borate, basiccopper phosphate, or mixtures thereof. The most preferred embodiments ofthe invention comprise particles comprising copper hydroxide, basiccopper carbonate, basic copper borate, basic copper phosphate, ormixtures thereof.

Coatings for the Copper-Containing and Zinc-Containing Particulates.

In any of the above-described embodiments, the copper-containingparticulates can further comprise one or more materials disposed on theexterior of the particles to inhibit dissolution of the underlyingsparingly soluble copper material at least for a time necessary toprepare the formulation and inject the prepared wood treatmentcomposition. Additionally or alternatively the acid-soluble particlesare coated with a substantially inert coating, for example a thin outercoating of e.g. copper phosphate or copper sulfide, or a coating of apolymeric material such as dispersants and/or stabilizers, or with athin hydrophobic coating of oil and/or of a liquid organic biocide, orany combination thereof. In one embodiment the particles are treatedwith a dispersing material which is substantially bound to theparticles.

The milled organic and inorganic particles described above are readilyslurried and injected into wood after the milling process. Generally,however, milling is done well before the particles are slurried andinjected. The particles may be shipped in a dry form or in a wet form.The milled particles may be transported to a site as a dry mix or as aconcentrated slurry, which is then formed into an injectable slurry, andthen after some indeterminate storage time the particles may be injectedinto wood. Some particulates in solution have a tendency to grow overtime. Others tend to agglomerate. Therefore, it is advantageous to havea coating on the particle to substantially hinder dissolution of theparticle while the particle is slurried, and to make the particlessubstantially non-interacting and non-agglomerating. But, the coatingshould not overly hinder dissolution of the particle in the wood matrix.

Generally, the discussion focuses on the preferred copper-containingparticulates, but the compositions and methods are equally applicable onthe zinc-containing and tin-containing particulates. The sparinglysoluble copper material, zinc material, and/or tin material can bestabilized by a partial or full coating of an inorganic salt. Themanufacturing process is amenable to the formation of a substantiallyinert inorganic coating on the particle that will be of such lowthickness that the coating will not substantially hinder particledissolution in the wood. The preferred coatings are very low solubilitymetal salts of the underlying metal cations, e.g., copper, zinc, or tin.Exemplary very low solubility salts include copper sulfide (Ksp ˜10⁻³⁶),copper(II) phosphate (Ksp ˜10⁻³⁷), and copper 8-quinolinolate (Ksp˜10⁻³⁰). The zinc and tin analogs are also very insoluble. The selectionbetween sulfide, 8-quinolinolate, and phosphate generally depends onwhich coating shows the greatest protection for the particularsubstantially crystalline (or amorphous sparingly soluble) material, atthe particular size distribution and particle morphology that may exist.A coating of a very low solubility salt can substantially arrest thedissolution/reprecipitation process by severely limiting the amount ofcopper that can dissolve. The coating, however, is mechanical protectiononly. Exposed portions of the underlying substantially crystalline (oramorphous sparingly soluble) copper-, zinc-, or tin-based particulatesare subject to dissolution. Further, the inorganic coating is generallyat most a few atoms to a few nanometers in depth.

The particles may be wet-milled using a very fine milling material and afluid containing a source of phosphate ions, or less preferably (becauseof odor and handling problems) sulfide ions. In one preferredembodiment, the wet milling process uses as the milling fluid acomposition comprising between a few hundred ppm of phosphate to about6% phosphate, for example between 0.1% phosphate to 3% phosphate. Smallamounts of phosphate will take hours or days to form a completelyprotective coating, while a more concentrated solution may form aprotective coating in minutes. Advantageously the milling liquid has apH between about 6 and about 9.5, for example between about 7 and about8.5. This high concentration of phosphate is not wasteful because themilling fluid can be re-used, and also because the milling fluid is arelatively small volume. Such milling of particles of inorganic copperand inorganic zinc in the phosphate-containing milling fluid, forexample for a time ranging from 5 minutes to 4 hours, typically from 10minutes to 30 minutes, will promote the formation of a thin coating ofcopper(zinc) phosphate over the sparingly soluble copper material. Asthe coating is probably only a few atoms in thickness, the coating willdissolve in good time within the wood so as not to impair exposure ofthe underlying sparingly soluble copper material in the wood.Alternatively, a source of sulfide or 8-quinolinolate can be added tothe milling liquid. Sulfide is again not preferred, for safety reasons.

In another embodiment, the copper-containing particles after milling canbe exposed to a rinse solution that contains between a few hundred ppmof phosphate to about 6% phosphate, for example between 0.1% phosphateto 3% phosphate.

The invention also embraces embodiments where particles aresubstantially free of an inorganic coating.

Copper-containing particles, zinc-containing particles, tin-containingparticles, and even solid substantially insoluble organic biocideparticles may additionally comprise an organic coating, e.g., a organiclayer that partially or completely covers the exterior surface area ofthe particulates. Indeed, in most preferred embodiments of theinvention, the surface of the particles has bound thereto at least somedispersants and/or stabilizers, and these qualify as an organiccovering. Generally such coatings are extremely thin, with a particulatecomprising for example between about 0.1% to about 50% by weight, moretypically from about 0.5% to about 10%, of the weight of theabove-mentioned sparingly soluble salts. The coating may cover only aportion of the exterior surface area. The organic coating advantageouslyis a thin layer of organic material that at least partially coats theparticulate and for a period of time reduces the tendency of thesparingly soluble copper, zinc, and/or tin salts in the particulates todissolve in the slurry. This organic coating can comprise a variety ofmaterials having a variety of functions over and above being an organiclayer acting as a protective layer temporarily isolating the sparinglysoluble salt from the aqueous carrier to slow dissolution ofparticulates in the slurry, including: 1) an organic biocide carrier, 2)dispersing/stabilizing agents, 3) wettability modifying agents, 3)substantially insoluble organic biocides, or any combinations thereof.The coating can comprise for example light oils, hydrophobic oils, anddehydrating oils; polymeric particles that are usually functionalizedwith for example carboxylate and or sulfonate moieties, organic biocidesincluding for example an amine, azole, triazole, or any other organicbiocides; dispersing agents and stabilizing agents/anti-coagulatingagents including for example an organic compound having one or morepolar functional groups which increase adherence, for example:mono-and/or poly-carboxylic acids that may be at least partiallyneutralized with a metal, or a film-forming polymer such as a sulfonatedionomer; a surfactant; amphoteric agents; or mixtures thereof. These andother organic and/or organometailic components that form an organiclayer will generally be referred to as a “hydrocarbon layer” or “organiccoating.”

An organic coating comprising oils may be formed by contactingparticulates with a hydrocarbon composition containing at least aportion of the materials to be deposited onto the exterior surface ofthe particle. The contacting may occur in a slurry or may be done with apaste of water-wetted particulates or may be done with driedparticulates. The less free water, the easier it is to promote adherencebetween the hydrocarbon composition to the particulates. Drying oils andsurface active agents such as stabilizers can also promote adherance oforganic layer to the particle. Incorporating some solvents, typicallypolar solvents, e.g., at least 10%, for example at least 30% or at least50% by weight of solvents such as one or more of alcohols, amides,ketones, esters, ethers, glycols, and such into the may help thehydrocarbon layer composition wet the particulates, and will allowthinner hydrocarbon layers to be deposited. Solvents are lower molecularweight and higher volatility than oils, and solvents may be strippedfrom the organic coating before slurrying the particles or during kilndrying of the wood. Advantageously, in one embodiment most of thesolvent of the hydrocarbon composition is volatile and is removed priorto injection of the particulates into the wood. This will leave a thinlayer of a more concentrated biocide in heavier oils and/or binders thanwas found in the hydrocarbon/biocide composition. The organic coatinggenerally becomes more adherent if the coated particulates are allowedto age, and or are subjected to heat, for example to 35 C or above for aperiod of an hour, for example.

2) Surface-Active Agents—The surface active agents are advantageouslyincluded in the liquid while milling, and such agents are similarlyuseful in the product. The numerous stabilizers and dispersants listedin with respect to milling are included here by reference. Agentsimproving the suspension and dispersion of the particulates includedispersants such as phenyl sulfonates, alkylnaphthalene sulfonates andpolymerized naphthalene sulfonates, polyacrylic acids and their salts,polyacrylamides, polyalkoxydiamine derivatives, polyethylene oxides,polypropylene oxide, polybutylene oxide, taurine derivatives and theirmixtures, and sulfonated lignin derivatives. Surfactants include anionicsurfactants, cationic surfactants, nonionic surfactants, or combinationsthereof. Polyethyleneimine can act as a surfactant or a stabilizer andwill also chelate copper. Dispersants can be used at 0.1% to 50%,preferably 0.5% to 20% or 5-10% of the particulate product.

Aqdvantageously, if there are a plurality of types of particles in aslurry, the surface active dispersants and stabilizers are compatibleand prevent the various types of particles from interacting oragglomerating.

3) Organic Biocides—As previously stated, the particles may be combinedwith one or more additional moldicides or more generally biocides, toprovide added biocidal activity to the wood or wood products. Theabsolute quantity of organic biocides incorporated into most woodtreatments is very low compared to the amount of inorganic salts, e.g.,copper salts. In general, the biocides are present in a useconcentration of from 0.1% to 20%, preferably 1% to 5%, based on theweight of the copper salts. The sparingly soluble copper-saltparticulates of this invention are typically expected to be added towood in an amount equal to or less than 0.25 pounds as copper per cubicfoot. The organic biocide(s) at a 4% loading relative to the copper arepresent at about 0.16 ounces or about 3 to 4 milliliters of biocide percubic foot. The organic biocides are often insoluble in water, which isthe preferred fluid carrier for injecting the wood preservativetreatment into wood, so getting adequate distribution of the biocidewithin the wood matrix is problematic. In prior art formulations, thewood preservative may be for example admixed in a large excess of oil,and the oil emulsified with water and admixed with the soluble copperfor injection into the wood. Problems arise if the injection is delayed,or if the slurry has compounds which break the emulsion, and the like.

In one embodiment, a substantial benefit is that a portion or all of theorganic biocides incorporated into the wood preservative treatment canadvantageously be coated on to the particulates. Preferred preservativetreatments comprise copper-based particles having one or more additionalorganic biocide(s) that are bound, such as by adsorption, to a surfaceof the particles. Wood and wood products may be impregnatedsubstantially homogeneously with copper-based particles of theinvention, each also comprising organic biocidal material bound to thesurface of the copper-based particles. By substantially homogeneously wemean averaged over a volume of at least a cubic inches, as on amicroscopic scale there will be volumes having particulates disposedtherein and other volumes within the wood that do not have particulatestherein. By adhering the biocides on particulates, a more evendistribution of biocide in ensured, and the copper is disposed with thebiocide and therefore is best positioned to protect the biocide fromthose bio-organisms which may degrade or consume the biocide. Thehomogenous distribution of preservative function within the wood or woodproduct is benefited. Finally, a formulation with biocide adhering toparticulates does not face the instability problems that emulsions faceduring the formulation and injection phases.

Alternately or additionally, the organic biocide can be contained inmilled injectable solid organic biocide particulates. Generally, such asmall quantity of organic biocides are required that the d₅₀ of theorganic biocides is advantageously between about 0.2 to about 0.8 timesthe d₅₀ of the sparingly soluble copper salts.

The biocides can be any of the known organic biocides. Exemplarymaterials having a preservative function include materials having atleast one of one or more: azoles; triazoles; imidazoles; pyrimidinylcarbinoles; 2-amino-pyrimidines; morpholines; pyrroles; phenylamides;benzimidazoles; carbamates; dicarboximides; carboxamides;dithiocarbamates; dialkyldithiocarbamates;N-halomethylthio-dicarboximides; pyrrole carboxamides; oxine-copper,guanidines; strobilurines; nitrophenol derivatives; organo phosphorousderivatives; polyoxins; pyrrolethioamides; phosphonium compounds;polymeric quaternary ammonium borates; succinate dehydrogenaseinhibitors; formaldehyde-releasing compounds; naphthalene derivatives;sulfenamides; aldehydes; quaternary ammonium compounds; amine oxides,nitroso-amines, phenol derivatives; organo-iodine derivatives; nitrites;quinolines such as 8-hydroxyquinoline including their Cu salts;phosphoric esters; organosilicon compounds; pyrethroids; nitroimines andnitromethylenes; and mixtures thereof.

Exemplary biocides include Azoles such as azaconazole, bitertanol,propiconazole, difenoconazole, diniconazole, cyproconazole,epoxiconazole, fluquinconazole, flusiazole, flutriafol, hexaconazole,imazalil, imibenconazole, ipconazole, tebuoonazole, tetraconazole,fenbuconazole, metconazole, myclobutanil, perfurazoate, penconazole,bromuconazole, pyrifnox, prochloraz, triadimefon, triadlmenol,triffumizole or triticonazole; pyrimidinyl carbinoles such as ancymidol,fenarimol or nuarimol; chlorothalonil; chlorpyriphos;N-cyclohexyldiazeniumdioxy; dichlofluanid; 8-hydroxyquinoline (oxine);isothiazolone; imidacloprid; 3-iodo-2-propynylbutyicarbamatetcbuconazole; 2-(thiocyanomethylthio) benzothiazole (Busan 30);tributyltin oxide; propiconazole; synthetic pyrethroids;2-amino-pyrimidine such as bupirimate, dimethirimol or ethirimol;morpholines such as dodemorph, fenpropidin, fenpropimorph, spiroxanin ortridemorph; anilinopyrimdines such as cyprodinil, pyrimethanil ormepanipyrim; pyrroles such as fenpiclonil or fludioxonil; phenylamidessuch as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace oroxadixyl; benzimidazoles such as benomyl, carbendazim, debacarb,fuberidazole or thiabendazole; dicarboximides such as chlozolinate,dichlozoline, iprdine, myclozoline, procymidone or vinclozolin;carboxamides such as carboxin, fenfuram, flutolanil, mepronil,oxycarboxin or thifluzamide; guanidines such as guazatne, dodine oriminoctadine; strobilurines such as azoxystrobin, kresoxim-methyl,metominostrobin, SSF-129, methyl2-[(2-trifluoromethyl)pyrid-yloxymethyl]-3methoxycacrylate or 2-[.alpha.{[(.alpha.-methyl-3-trifluoromethyl-benzyl)imino]oxy}-o-toly]gly oxylicacid-methylester-O-methyloxime (trifloxystrobin); dithiocarbamates suchas ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb or ziram;N-halomethylthio-dicarboximides such as captafol, captan, dichlofluanid,fluorormide, folpet or tolfluanid; nitrophenol derivatives such asdinocap or nitrothal-isopropyl; organo phosphorous derivatives such asedifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos ortoclofos-methyl; and other compounds of diverse structures such asaciberolar-S-methyl, anilazine, blasticidin-S, chinomethionat,chloroneb, chlorothalonil, cymoxanil, dichlone, dicomezine, dicloran,diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone,fenamidone, fentin, ferimzone, fluazinam, flusuffamide, fenhexamid,fosetyl-alurinium, hymexazol, kasugamycin, methasuifocarb, pencycuron,phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen,quintozene, sulfur, triazoxide, tricyclazole, triforine, validamycin,(S)-5-methyl-2-methylthio-5-phenyl-3-phenyl-amino3,5-dihydroimidazol-4-one(RPA 407213),3,5-dichloro-N-(3chlro-1-ethyl-1-methyl-2-oxopropyl)₄-methylbenzamide(RH7281), N-alkyl-4,5-dimethyl-2-timethylsilythiophene-3-carboxamide(MON 65500),4-chloro-4-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfon-amide(IKF-916),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4dichlorophenoxyy)-propionamide (AC382042), or iprovalicarb (SZX 722). Also included are the biocidesincluding pentachlorophenol, petroleum oils, phenothrin, phenthoate,phorate, as well as trifluoromethylpyrrole carboxamides andtrifluoromethylpyrrolethioamides described in U.S. Pat. No. 6,699,818;Triazoles such as Amitrole, azocylotin, bitertanol, fenbuconazole,fenchlorazole, fenethanil, fluquinconazole, flusilazole, flutriafol,imibenconazole, isozofos, myclobutanil, metconazole, epoxyconazole,paclobutrazol,(.+−.))-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole,triticonazole, uniconazole and their metal salts and acid adducts;Imidazoles such as Imazalil, pefurazoate, prochloraz, triflumizole,2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,thiazolecarboxanilides such as2′,6′-dibromo-2-methyl-4-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxanilide;azaconazole, bromuconazole, cyproconazole, dichlobutrazol, diniconazole,hexaconazole, metconazole, penconazole, epoxyconazole, methyl(E)-methoximino>.alpha.-(o-tolyloxy)-o-tolyl)!acetate, methyl(E)-2-{2->6-(2-cyanophenoxy)-pyrimidin-4-yl-oxy!phenyl}-3-methoxyacrylate,methfuroxam, carboxin, fenpiclonil,4(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile,butenafine, 3-iodo-2-propinyl n-butylcarbamate; triazoles such asdescribed in U.S. Pat. Nos. 5,624,916; 5,527,816; and 5,462,931; thebiocides described in U.S. Pat. No. 5,874,025;5-[(4-chlorophenyl)methyl]-2,2-dimethyl-1-(1H-1,2,4-triazol-1-yl-methyl)cyclopentanoland imidacloprid,1-[(6-chloro-3-pyridinyl)-methyl]-4,5-dihydro-N-nitro-1H-imidazole-2-amine;Methyl(E)-2->2->6-(2-cyanophenoxy)pyrimidin-4-yloxy!phenyl!3-methoxyacrylate,methyl(E)-2->2->6-(2-thioamidophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2->6-(2-fluorophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2->6-(2,6-difluorophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2->3-(pyrimidin-2-yloxy)phenoxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2->3-(5-methylpyrimidin-2-yloxy)-phenoxy!phenyl!-3-methoxy-acrylate,methyl(E)-2->2->3-(phenylsulphonyloxy)phenoxy!phenyl-3-methoxyacrylate,methyl(E)-2->2->3-(4-nitrophenoxy)phenoxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2-phenoxyphenyl-3-methoxyacrylate,methyl(E)-2->2-(3,5-dimethylbenzoyl)pyrrol-1-yl-3-methoxyacrylate,methyl(E)-2->2-(3-methoxyphenoxy)phenyl!-3-methoxyacrylate,methyl(E)-2>2-(2-phenylethen-1-yl)-phenyl-3-methoxyacrylate,methyl(E)-2->2-(3,5-dichlorophenoxy)pyridin-3-yl!-3-methoxyacrylate,methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate,methyl(E)-2-(2->3-(alphahydroxybenzyl)phenoxy!phenyl)-3-methoxyacrylate,methyl(E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate,methyl(E)-2->2-(3-n-propyloxyphenoxy)phenyl-3-methoxyacrylate,methyl(E)-2->2-(3-isopropyloxyphenoxy)phenyl!-3-methoxyacrylate,methyl(E)-2->2->3-(2-fluorophenoxy)phenoxy!phenyl!-3-methoxyacrylate,methyl(E)-2->2-(3-ethoxyphenoxy)phenyl-3-methoxyacrylate,methyl(E)-2->2-(4-tert-butylpyridin-2-yloxy)phenyl!-3-methoxyacrylate;Fenfuram, furcarbanil, cyclafluramid, fummecyclox, seedvax, metsulfovax,pyrocarbolid, oxycarboxin, shirlan, mebenil (mepronil), benodanil,flutolanil; Benzimidazoles, such as carbendazim, benomyl, furathiocarb,fuberidazole, thiophonatmethyl, thiabendazole or their salts; Morpholinederivatives, such as tridemorph, fenpropimorph, falimorph, dimethomorph,dodemorph; aldimorph, fenpropidine and their arylsulphonates, such as,for example, p-toluenesulphonic acid and p-dodecylphenylsulphonic acid;Benzothiazoles, such as 2-mercaptobenzothiazole; Benzamides, such as2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide; oxazolidine,hexa-hydro-5-triazines, N-methylolchloroacetamide, paraformadehyde,nitropyrin, oxolinic acid, tecloftalam;Tris-N-(cyclohexyldiazeneiumdioxy)-aluminium,N-(cyclohexyldiazeneiumdioxy)-tributyltin,N-octyl-isothiazolin-3-one,4,5-trimethylene-isothiazolinone,4,5-benzoisothiazolinone,N-methylolchloroacetamide; Pyrethroids, such as allethrin, alphamethrin,bioresmethrin, byfenthrin, cycloprothrin, cyfluthrin, decamethrin,cyhalothrin, cypermethrin, deltamethrin,alpha-cyano-3-phenyl-2-methylbenzyl2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)cyclopropane-carboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permethrin, resmethrin and tralomethrin; Nitroimines andnitromethylenes, such as1->(6-chloro-3-pyridinyl)-methyl!-4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid),N->(6-chloro-3-pyridyl)methyl-!N.sup.2-cyano-N.sup.1-methylacetamide(NI-25); Quaternary ammonium compounds, such as didecyldimethylammoniumsalts; benzyldimethyltetradecylammonium chloride,benzyldimethyldodecylammonium chloride, didecyldimethaylammoniumchloride; Phenol derivatives, such as tribromophenol, tetrachlorophenol,3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol,dichlorophene, o-phenylphenol, m-phenylphenol, p-phenylphenol,2-benzyl-4-chlorophenol and their alkali metal and alkaline earth metalsalts; iodine derivatives, such as diiodomethyl p-tolyl sulphone,3-iodo-2-propinyl alcohol, 4-chloro-phenyl-3-iodopropargyl formal,3-bromo-2,3-diiodo-2-propenyl ethylcarbamate, 2,3,3-triiodoallylalcohol, 3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinylcyclohexyl-carbamate, 3-iodo-2-propinyl phenylcarbamate; Microbicideshaving an activated halogen group, such as chloroacetamide, bronopol,bronidox, tectamer, such as 2-bromo-2-nitro-1,3-propanediol,2-bromo-4′-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide,1,2-dibromo-2,4-dicyanobutane, .beta.-bromo-.beta.-nitrostyrene; andcombinations thereof. These are merely exemplary of a few classes of theknown and useful biocides, and the list could easily extend for pages.

Preferred biocides for wood preservation include quaternary ammoniumcompounds including for example didecyldimethylammonium salts;azoles/triazoles including for example N-alkylated tolytriazoles,metconazole, imidacloprid, hexaconazole, azaconazole, propiconazole,tebuconazole, cyproconazole, bromoconazole, and tridemorph tebuconazole;moldicides; HDO available commercially by BASF, or mixtures thereof.

Exemplary millable biocides include Chlorothalonil, Metaldehyde,triphenyltin hydroxide, Maneb, Mancozeb, Zineb, Ziram, and/or Ferbam,and wherein the milled organic biocide product preferably has a volumemean diameter d₅₀ between about 0.1 and 0.3 microns and a d₉₀, such that90 volume percent of the product has a diameter of the d90 or less, ofless than about 3 times the d₅₀.

Generally, millable biocides can be found in each of imidazolinones,sulfonylureas, triazolopyrimidine sulfonamides, aryloxyphenoxypropionates, triazines, chloroacetanilides, pyrazoles, and diphenylethers. Specific examples of millable biocides, some of which are usefulfor wood preservative applications and some of which are useful infoliar applications, include amitraz, azinphos-ethyl, azinphos-methyl,benzoximate, fenobucarb, gamma-HCH, methidathion, deltamethrin, dicofol,dioxabenzafos, dioxacarb, dinobuton, endosulfan, bifenthrin, binapacryl,bioresmethrin, chlorpyrifos, chlorpyrifos-methyl, EPNethiofencarb,cyanophos, cyfluthrin, tetradifon, cypermethrin, tralomethrin,bromophos, N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-xylidene,2,4-parathion methyl, bromopropylate, butacarboxim, butoxycarboxin,chlordimeform, phosalone, chlorobenzilate, phosfolan, chloropropylate,phosmet, chlorophoxim, promecarb, fenamiphos, quinalphos, resmethrin,temephos, pirimiphos-ethyl, tetramethrin, pirimiphos-methyl, xylylcarb,profenofos, acrinathrin, propaphos, allethrin, propargite, benfuracarb,propetamphos, bioallethrin, pyrachlofos, bioallethrin S, tefluthrin,bioresmethrin, terbufos, buprofezin, tetrachlorinphos, chlorfenvinphos,tralomethrin, chlorflurazuron, triazophos, chlormephos, pyrachlofos,tefluthrin, terbufos, tetrachlorinphos, cycloprothrin, betacyfluthrin,cyhalothrin, cambda-cyhalothrin, tralomethrin, alpha-cypermethrin,triazophos, beta-cypermethrin, cyphenothrin, demeton-S-methyl,dichlorvos, disulfoton, edifenphos, empenthrin, esfenvalerate,ethoprophos, etofenprox, etrimphos, fenazaquin, fenitrothion,fenthiocarb, fenpropathrin, fenthion, fenvalerate, flucythrinate,flufenoxuron, tau-fluvalinate, formothion, hexaflumuron, hydroprene,isofenphos, isoprocarb, isoxathion, malathion, mephospholan, methoprene,methoxychlor, mevinphos, permethrin, phenothrin, phenthoate, benalaxyl,biteranol, bupirimate, cyproconazole, carboxin, tetraconazole,dodemorph, difenoconazole, dodine,dimethomoph, fenarimol,diniconazole,ditalimfos, ethoxyquin, myclobutanil, etridiazole, nuarimol,fenpropidin, oxycarboxin, fluchloralin, penconazole, flusilazole,prochloraz, imibenconazole, tolclofos-methyl, myclobutanil, triadimefon,propiconazole, triadimenol, pyrifenox, azaconazole, tebuconazole,epoxyconazole, tridemorph, fenpropimorph, triflumizole, 2,4-D esters,diclofop-methyldiethatyl, 2,4-DB esters, dimethachlor, acetochlor,dinitramine, aclonifen, ethalfluralin, alachlor, ethofumesate,anilophos, fenobucarb, benfluralin, fenoxapropethyl, benfuresate,fluazifop, bensulide, fluazifop-P, benzoylprop-ethyl, fluchloralin,bifenox, flufenoxim, bromoxynil esters, flumetralin, bromoxynil,flumetralin, butachlor, fluorodifen, butamifos, fluoroglycofen ethyl,butralin, fluoroxypyr esters, butylate, carbetamide, chlomitrofen,chlorpropham, cinmethylin, clethodim, clomazone, clopyralid esters, CMPPesters, cycloate, cycloxydim, desmedipham, dichlorprop esters, flurecolbutyl, flurochloralin, haloxyfop, ethoxyethyl, haloxyfop-methyl, ioxynilesters, isopropalin, MCPA esters, mecoprop-P esters, metolachlor,monalide, napropamide, nitrofen, oxadiazon, oxyfluorfen, pendimethalin,phenisopham, phenmedipham, picloram esters, pretilachlor, profluralin,propachlor, propanil, propaquizafop, pyridate, quizalofop-P, triclopyresters, and tridiphane.

Of course, organic biocides can be coated onto ground organicparticulates in much the same manner that they can be coated ontoinorganic salt particles. This ability allows a formulator to includefor example a primary organic biocide and one or more secondary organicbiocides on the same particle. This is particularly advantageous if thesecondary biocides are targeted specifically toward one or morebio-organisms that degrade the primary biocide.

It can be seen that the ability to formulate very small particulates,and to optionally coat these particulate with biocides as well as withstabilizers and dispersants, opens a wide variety of possibilities forthe use of biocides in the fields of foliar applications, woodpreservation, anti-fouling paints and coatings, and even biocidalcoverings such as roofs and walls. Generally, the differences betweenfoliar applications and wood preservatives are: the foliar applicationsare subject to more UV light and greater water flux; foliar applicationsare typically not intended to have a lifetime greater than one year,while wood preservative treatments try to attain 20 or more yearlifespans, and the particle size distribution in wood preservation mustbe much narrower, particularly on the upper end of the particle sizedistribution.

For foliar and for wood preservative applications, a slurry compositionis preferred, for example a slurry comprising: a liquid carriercomprising stabilizers and dispersants; and one or more of:

-   -   1) injectable solid particulates comprising a substantially        insoluble solid organic biocide;    -   2) injectable solid particulates comprising a substantially        insoluble solid organic biocide and coated with a thin organic        layer which may comprise a substantially insoluble organic        biocide;    -   3) injectable solid particulates comprising a sparingly soluble        copper salts;    -   4) injectable solid particulates comprising a sparingly soluble        copper salts and coated with a thin organic layer which may        comprise a substantially insoluble organic biocide;    -   5) injectable solid particulates comprising a sparingly soluble        zinc (and/or tin) salts;    -   6) injectable solid particulates comprising a sparingly soluble        zinc (and/or tin) salts and coated with a thin organic layer        which may comprise a substantially insoluble organic biocide;        inert carrier particles coated with a organic layer comprising a        substantially insoluble organic biocide, and    -   optionally but disfavored a soluble copper amine.        The inert carrier particulates can be bioactive zeolite-based        particles, alumina particles, and the like. An exemplary        particle comprises copper hydroxide having an average particle        diameter of less than about 500 nanometers, for example less        than about 250 nanometers, or less than about 200 nanometers, as        measured by Stokes Law settling velocity. Preferably, the        average particle diameter is at least 25 nanometers, for        example, at least 50 nanometers. The particle size distribution        of the particulates in one embodiment is such that at least        about 30% by weight of the particulates have an average diameter        between about 0.07 microns and about 0.5 microns, or preferably        at least about 50% by weight of the particulates have an average        diameter between about 0.1 microns and about 0.4 microns.

The particle size distribution of the particulates in one embodiment issuch that at least about 30% by weight of the particulates have anaverage diameter between about 0.02 microns and about 0.4 microns, orpreferably at least about 50% by weight of the particulates have anaverage diameter between about 0.05 microns and about 0.3 microns. Themetallic copper and/or metallic zinc particiulates have both a minorbiocidal effect and also an anti-corrosion effect. The amount of metal,either copper, zinc, or both, in the anti-corrosion metallicparticulates can range from about 1 part to about 25 parts per 100 partsof particulates comprising slightly soluble copper salts. Themetal-containing particulates in this variant of the invention areprimarily anti-corrosion additives, though they will have some biocidaleffect. Further, organic biocides can be readily coated onto thesemetal-containing particulates.

In a preferred embodiment the sparingly soluble copper salts in thecopper-containing particulates comprise or consist essentially of one ormore copper salts selected from copper hydroxides; copper carbonates,basic (or “alkaline”) copper carbonates; basic copper sulfates includingparticularly tribasic copper sulfate; basic copper nitrates; copperoxychlorides (basic copper chlorides); basic copper sulfates, basiccopper borates, and mixtures thereof. In one embodiment, thecopper-based particles comprise a substantially crystalline coppercompound. At least about 20%, 30%, 50%, or 75% of the weight of thecopper-based particles may be composed of the substantially crystallinecopper compound.

The zinc analogs of the above are useful for the zinc-based particulatesof the alternate embodiments of the invention. In one embodiment thecopper-based particulate material can further comprise one or more ofcrystalline zinc salts selected from zinc hydroxide; zinc oxides; zinccarbonate; zinc oxychloride; zinc fluoroborate; zinc borate, zincfluoride, or mixture thereof.

In preferred embodiments of this invention, the slurry is substantiallyfree of alkanolamines, e.g., the slurry comprises less than 1%alkanolamines, preferably less than 0.1% alkanolamines, or is totallyfree of alkanolamines.

In preferred embodiments of this invention, the slurry is substantiallyfree of amines, e.g., the slurry comprises less than 1% amines,preferably less than 0.1% amines, or is totally free of amines, with theproviso that amines whose primary function is as an organic biocide areexcluded. Generally, if amines are included, they form dispersants andstabilizers, and they are used at the lowest practicable concentrations.

In preferred embodiments of this invention, the slurry is substantiallyfree of ammonium compounds (e.g., ammonium hydroxide), e.g., the slurrycomprises less than 1% ammonia, preferably less than 0.1% ammonia, or istotally free of ammonium compounds, with the proviso that ammoniumcompounds whose primary function is as an organic biocide are excluded.

In preferred embodiments of this invention, the slurry is substantiallyfree of solvents, e.g., the slurry comprises less than 1% organicsolvents, preferably less than 0.1% organic solvents, or is totally freeof organic solvents.

The loading of the particulates in the slurry will depend on a varietyof factors, including the desired copper loading in the wood, theporosity of the wood, and the dryness of the wood. Calculating theamount of copper-based particulates and/or other particulates in theslurry is well within the skill of one of ordinary skill in the art.Generally, the desired copper loading into wood is between 0.025 andabout 0.5 pounds copper per cubic foot of wood.

In a preferred embodiment the liquid carrier consists essentially ofwater and optionally one or more additives to aid particulatedispersion, pH maintenance, interfacial tension (surfactants), andparticle stability (anticoagulants). In another embodiment the carrierconsists essentially of water and optionally one or more additives toaid particulate dispersion, pH maintenance, interfacial tension,stabilizers/anticoagulants, and oil-in-water emulsion of oil containingorganic biocides dissolved therein.

Advantageously the pH of the liquid carrier is between about 7 and about11, for example between about 7.5 to about 9, or between about 8 andabout 8.5. Alternately, the pH of the injectable slurry is between pH 6and 11, preferably between 7 and 10, for example between 7.5 and about9.5. Acidic pH slurries are not preferred because several of thesparingly soluble copper salts of this invention have a highersolubility at lower pH. The pH can be adjusted with alkali hydroxides,alkali carbonates, less preferably with alkaline earth oxides orhydroxides; and even less preferably with amines including ammoniumhydroxide. Alkaline earth bases are less preferred because if carbondioxide or carbonates are present in solution, there is a possibility ofprecipitation, for example of calcite. Such precipitation may createundesired plugging of the wood during injection. The preferredingredients to increase the pH is an alkali hydroxide, e.g., sodiumhydroxide or potassium hydroxide or alkali carbonate, or both.

It may be advantageous to add basic alkali phosphate, basic alkaliborate, or the monoacid forms thereof, or any combinations thereof, tothe liquid carrier to increase the pH and provide some bufferingcapacity. The slurry is beneficially buffered, by for example addingphosphate at 5 ppm to 500 ppm. The higher concentrations of phosphatesmay be beneficial if the particulates do not have any coatings formedthereon, as the soluble phosphate ions will discourage dissolution ofthe copper salts from the particulates into the liquid carrier. Solubleborates can be added in an amount from about 5 ppm to about 2000 ppm inthe slurry, where less than 5 ppm has little effect and more than 2000ppm is cost-prohibitive. Borates have both a biocidal activity and afire-retardant activity.

In one embodiment the slurry comprises between 50 and 800 ppm of one ormore scale precipitation inhibitors, particularly organophosphonates.Alternately or additionally the slurry may contain between about 50 andabout 2000 ppm of one or more chelators. Both of these additives aremeant to inhibit precipitation of salts such as calcium carbonate andthe like, where the source of calcium may be from the water used to makeup the slurry. The preferred inhibitors are hydroxyethylidenediphosphonic acid (HEDP), diethylenetriamine-pentamethylenephosphonicacid (DTPMP), and/or 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC).If the preservative is in a slurry concentrate, the slurry shouldcomprise between 10 mmoles and 100 mmoles/L of HEDP, or between 30mmoles and 170 mmoles/L of PBTC or DTPMP. Mixtures of inhibitors arepreferred, as concentrates may have more inhibitor than can readily besolubilized therein. If the preservative is in a solid form, thepreservative should comprise between about 0.1 to about 1 mole HEDP perkg of particulates, or between about 0.17 to about 2 mole PBTC and/orDTPMP per kg of particulates.

Increased corrosion of metal fillings has been observed in formulationsusing soluble copper preservatives, as opposed to the prior art CCAformulations. The slurry of this invention, having a basic pH and havingvery low amine content, is expected to reduce the corrosion rate overthat seen with soluble copper. There are additional treatment that canhelp reduce corrosion. The presence of phosphate salts in both theinorganic sparingly soluble particulates of some embodiments of theinvention, and also optionally dissolved in the liquid phase of theslurry, is expected to reduce corrosion. The presence of carbonates andhydroxides, in both the inorganic sparingly soluble particulates ofpreferred embodiments of the invention, and also optionally dissolved inthe liquid phase of the slurry, is expected to reduce corrosion.Eliminating amines, especially the large quantity of amines complexedwith the copper in currently used formulations, is expected to reducecorrosion and mold.

Preferred preservative materials inhibit organisms that may be resistantto copper-based preservatives. Moldicides useful in wood or wood productpreservation are also preferred organic biocides. If the woodpreservative treatment will comprise substantially insoluble organicbiocides, these substantially insoluble organic biocides may bepartially or fully coated onto the milled injectable sparingly solublecopper-containing particulates, sparingly soluble zinc-containingparticulates, sparingly soluble tin-containing particulates, or mixturesthereof. The substantially insoluble organic biocides may alternativelyor additionally be present as milled, injectable particulatesindependent of the milled injectable inorganic salt particulates.Substantially insoluble organic biocides may be coated on a milledinjectable particle of a different organic biocide. Alternatively oradditionally, these biocides may be partially or fully coated onto theavailable surface area of an inert particulate carrier. Alternatively,the organic biocides can be placed in a oil in water emulsion andinjected as in the prior art, and a portion of the emusion will end upcoating particles.

The slurry can advantageously contain one or more additives to aidwetting, for example surfactants. Surfactants may be in solution, oralternatively may bind to the surface, in which case they aresurface-active agents and may function as stabilizers or dispersants.Preferred dispersing agents include a surface active portion thatinteracts with the copper-containing particle and a second preferablydifferent portion, which operates to inhibit irreversible agglomerationof the copper-based particles. For example, a polyacrylate dispersingagent may include at least one carboxyl group capable of associating,such as electrostaticaly, with a copper-containing particle and asecond, hydrophobic portion that may operate to inhibit the permanentagglomeration of the copper-containing particles. Exemplary dispersingagents may include at least one of a surfactant, a polyacrylate, apolysaccharide, a polyaspartic acid, a polysiloxane, and a zwitterioniccompound. Exemplary compounds useful as dispersing agents are discussedin the section relating to milling.

In one embodiment of the invention, the copper-based particles maycomprise a polymer. In this embodiment, the ratio of the weight ofcopper present in the particles to polymer present in the particles maybe at least about 1 to 1, for example at least about 2 to 1, 4 to 1, 5to 1, 7 to 1, or at least about 10 to 1. For example, if ratio of theweight of copper present in the particles to the weight of polymerpresent in the particles is at least about 2 to 1, the particlescomprise at least about twice as much copper by weight as polymer.Another aspect of the invention relates to a preservative useful forwood or wood products, the preservative preferably comprising apreferably aqueous suspension of copper-based particles. If a polymericdispersing agent is present in the suspension, the ratio of the weightof copper present in the copper-based particles of the suspension to theweight of dispersing agent present in the suspension may be at leastabout 1 to 1, for example at least about 5 to 1, 10 to 1, 15 to 1, 20 to1 or at least about 30 to 1.

Dispersing agents aid particulate dispersion and to prevent aggregationof particulates. Sub-micron sized particulates have a tendency to formmuch larger aggregates. Aggregates as used herein are physicalcombinations of a plurality of similarly-sized particles, often broughttogether by VanDerWaal's forces or electrostatic forces. If aggregatesare allowed to form they often can age into a stable aggregate that cannot be readily broken up by mechanical agitation, for example byvigorous stirring of a slurry. Such aggregates may grow to a size wherethe aggregates are not readily injectable, or may be of a size to makethe aggregates visible, therefor giving undesired color. In preferredembodiments of the invention at least 30%, preferably at least 60%, morepreferably at least 90% by weight of the substantially crystallinecopper-based particulates in a slurry are mono-disbursed, e.g., are notin aggregates. Further, the particles advantageously do not tent toaglomerate when injected into the wood. To prevent particulates fromagglomerating, the concentrated slurry or paste may comprise cationic,anionic, and/or non-ionic surfactants; emulsifiers such as gelatine,casein, gum arabic, lysalbinic acid, and starch; and/or polymers, suchas polyvinyl alcohols, polyvinyl pyrrolidones, polyalkylene glycols andpolyacrylates, in quantities of 0.1 to 20% by weight, based on theweight of the particulates.

The slurry formulations mentioned can be prepared in a manner known perse, for example by mixing the active compounds with the liquid carrier,and including emulsifier, dispersants and/or binders or fixative, andother processing auxiliaries. Particulates can be provided in aconcentrated slurry, in a very concentrated paste, as dry particulates,as coated dry particulates, as part of a dry pre-mix, or any combinationthereof.

Slurry Concentrate—If the wood treatment is to be manufactured, stored,or transported in a wetted form, it is beneficially in a concentratedform to minimize the volume and expense of handling water. Preferablythe concentrated slurry or paste (for shipping and storing, for example,comprises between 5% and 80% by weight, for example between about 15%and 40%, of sparingly soluble copper-containing particulates, sparinglysoluble zinc-containing particulates, sparingly soluble tin-containingparticulates, or mixtures thereof, optionally with 0.1% to 10% ofpariculates of organic biocides, with the remainder of the concentratedslurry or paste beneficially being a fluid carrier. The concentratedslurry or paste may further comprise solid particulates that arecarriers for one or more organic biocides, solid particulates comprisingmetallic copper and/or zinc as corrosion inhibitors, or both. The fluidcarrier beneficially comprises one or more additives as discussed forthe slurry, including anti-oxidants, surfactants, disbursing agents,other biocidal salts and compounds, chelators, corrosion inhibitors,e.g., phosphate and/or borate salts, alkali metal hydroxides and/orcarbonates, antifreeze, and the like. The concentration of theseadditives will depend in part on the degree to which the slurry isexpected to be diluted to make a commercially usefull injectable slurryhaving the proper copper loading for the types of wood.

The moisture content of copper-based particles of the invention may bereduced, such as by drying, one or more dispersing agents may be used toinhibit irreversible agglomeration of reduced moisture particles of theinvention. The reduced moisture particles may be diluted, such as byhydration with water or combination with another liquid. Generally,dilution may be with water, beneficially fresh water.

Another aspect of the invention relates to an agglomeration comprising aplurality of copper-containing particles, organic biocide-containingparticles, or both, and dispersing agents. The agglomeration may alsoinclude one or more materials additional to the copper-based particlesthat also provide a wood or wood product preservative function. Theagglomeration may have a liquid content (excluding any additionalpreservative material that may be present) of less than 75% by weight,for example, of less than about 50%, less than about 25%, less thanabout 15%, or less than about 5% by weight. The liquid may be water. Theagglomeration may be diluted and/or dispersed in water with mixing oragitation, such as mechanically or ultrasonically.

As in the injectable slurry itself, the d₉₉, and preferably thed_(99.5), should be less than 1 micron, more preferably less than about0.6 microns. Advantageously the at least about 30% by weight of theparticulates have an average diameter between about 0.07 microns andabout 0.5 microns. In a preferred embodiment, at least about 50% byweight of the particulates have an average diameter between about 0.1microns and about 0.4 microns.

Dry Particulates and Dry Mix For Slurry—The particulates of thisinvention can be formulated and transported as a dry material, e.g., asa wettable powder, as dispersible granules, and even as larger tablets.The wettable powder, dispersible granules, or tablets advantageouslycomprise the biocidal particulates and those additives such as aredescribed as being present in the slurry, including for exampleanti-oxidants, surfactants, disbursing agents/stabilizing agents,chelators such as salts of ETDA, basic compounds, sequestrants such assalts of HEDP, and the like. The additives can be coated onto thesparingly soluble copper-based particulates and/or can be formed fromsecond particulates. The dry-mix material advantageously has allnecessary components in a single mix, and each component is present in arange that is useful when the dry mix is formed into a sprayable orinjectable slurry. The mixture may optionally but preferably incorporatea granulating material, which is a material that when wet holds aplurality of particulates together in the form of a granule or tablet,but that dissolves and releases the individual particulates on beingadmixed with the liquid carrier. Granules are preferred because of dustproblems and also the ease of measuring and handling a granular mixture.Granulating agents can be simple soluble salts, for example alkalicarbonates, that are sprayed onto or otherwise is admixed with theparticulate material.

One example of a biocide composition in granular or tablet form, whichrapidly disintegrates and disperses in water, includes, e.g., about 50parts particulate biocide, about 10 to about 40 parts salts, preferablycarbonate and/or bicarbonate salts, about 1 to about 20 parts solidchelators/sequestrants, about 5 to about 50 parts stabilizers and/ordispersants, and up to about 20 parts filler. Another exemplarydissolvable biocide granule comprises: 1) about 50-75% of a firstfinely-divided (submicron) particulate biocides, which may be a biocidalinorganic sparingly soluble copper salt, such as is produced by theprocesses of this invention; 2) optionally about 7-15% of a secondparticulate biocide, which may include particulates of solid essentiallywater-insoluble organic biocide; 3) about 2-30% of a stabilizer and/ordispersing agent; 4) about 0.01-10% of a wetting agent; 5) about 0-2% ofan antifoaming agent; 6) about 0-5% of a diluent; and optionally 7)about 0-5% of a chelating agent. One embodiment of the invention relatesto a dry mix material having a copper content of at least about 8% byweight. A preferred material includes a plurality of copper-containingparticles. The material may be shipped, such as in granular form, to alocation at which the material is prepared for use a wood preservative.The material may also comprise at least one of a wetting agent, adispersing agent, a diluent which may be a particulate comprisingorganic biocides thereon, an antifoaming agent, and an additionalmaterial having a biocide function.

One embodiment of the invention relates to a dry material having acopper content of at least about 15% by weight. A preferred materialincludes a plurality of copper-containing particles, which may be in theform of granules. The material also comprises at least one of a wettingagent, a dispersing agent, a diluent, an antifoaming agent, and anadditional material having a biocide function. In one embodiment, thematerial is a granular material comprising about 50% to 70%, for example58% copper hydroxide or other sparingly soluble copper salts, about 10%to 25%, for example 18% of a dispersing agent, such as Borresperse NA,about 1 to 8%, e.g., about 4% of a wetting agent, such as Morwet EP, andabout 10% to about 30% filler, e.g., about 20% attapulgite clay, such asDiluex A; optionally from 0.05% to 7% alkali hydroxides, alkalicarbonates, alkali phophates, and/or alkali borates; optionally 0.05% to5% salts of a sequestrant, for example HEDP, and optionally from 0.05%to 2% antifoaming agents.

In one embodiment, the dry-mix material is a granular materialcomprising about 40 to about 80% by weight of a sparingly soluble coppersalt, e.g., copper hydroxide, about 5% to about 30% of a dispersingagent, such as Borresperse NA, about 1% to about 10% of a wetting agent,such as Morwet EP, and about 5% to about 30% of a inert particulatefiller which may additionally comprise organic biocides absorbedthereon, e.g., attapulgite clay, such as Diluex A. In one embodiment,the material is a granular material comprising about 58% copperhydroxide, about 18% of a dispersing agent, such as Borresperse NA,about 4% of a wetting agent, such as Morwet EP, and about 20%attapulgite clay, such as Diluex A.

Another aspect of the invention relates to material comprising a coppercontent of at least about 15%, for example, at least about 20%, such asat least about 30% by weight. In one embodiment, the material may have acopper content of about 35% by weight. The material may have a coppercontent of less than about 50%, for example, less than about 45%, suchas less than about 40% by weight. Preferably, the material comprises aplurality of copper-based particles, which may contribute substantiallyall of the copper content of the material. The material may comprise aplurality of granules each comprising a plurality of copper-basedparticles. The copper-based particles, such as a surface thereof, may beassociated with a dispersing agent.

In one embodiment, the material comprises A) about 30% to 70% by weightof a slightly soluble copper salt, e.g., copper hydroxide, for example,about 35% to 65%, such as about 38% to about 61% of a slightly solublecopper salt, in particulate form; B) about 10% to 35% by weight, such asabout 15% to about 30% of at least one dispersing agent, e.g.,lignosulfonates or polyacrylates; C) between about 2.5% to 20% byweight, such as about 5% to 15% of at least one wetting agent, forexample, a surfactant, e.g., Morwet EP available from Barton Solvents,Inc.; D) between about 5% to about 25% by weight, such as about 10% to20% of at least one diluent, for example soluble and insoluble diluents,such as those used in agricultural products, e.g., clay, such as anattapulgite clay, or particulate carrier particles comprising organicbiocide; E) between about 0.05% to 7.5% by weight, such as about 0.1% toabout 5%, of at least one antifoam agent; and optionally F) about 2.5%to about 25%, alternatively less than about 7.5%, such as less thanabout 5% by weight, of water.

The material may be shipped, such as in granular form. The material ofthe invention offers reduced shipping costs and improved ease ofhandling compared to known preservative materials. A user may receivethe material and, if granules are present, disperse the granules,thereby preparing a flowable material comprising a plurality ofcopper-based particles. The material may be diluted, for example byusing water or other liquid. The copper-based particles may be injectedinto wood and/or wood materials as a preservative. Mechanical agitationand/or mixing may be used to disperse the granules.

Upon dispersing the material, wood or wood products may be treated withthe dispersed material, such as by subjecting the wood or wood productsto vacuum and or pressure in the presence of the dispersed material.Upon dispersing granules of the material, dispersed copper-basedparticles preferably remain suspended for at least about 30 minuteswithout further agitation, preferably, even in standard hard waterhaving a hardness of about 342 ppm. Once dispersed, fifty percent of thedispersed copper-based particles may have diameters less than about 1micron, for example, less than about 0.5 micron, such as less than about0.25 micron. In one embodiment, 50% of the dispersed copper-basedparticles have diameters less than about 0.2 micron, for example, 50% ofthe dispersed copper-based particles have diameters of about 0.1 micron.

The copper-based material may comprise additional material providing awood preservative and/or biocide function. For example, in oneembodiment the material comprises a plurality of copper-based particlesand a co-biocide. Exemplary organic co-biocides may include, forexample, one or more of a triazole compound, a quarternary amine, and anitroso-amine.

One object of the invention is to provide an effective, injectablecopper-based particulate preservative treatment that has leachingcharacteristics lower than copper amine treatments. Generally, leachrate tests involve high leachant rates so the leachant can notequilibrate with the sparingly soluble salts, and therefore measuredleach rates from particulates are expected to be low compared to leachrates from more quiescent systems. By “leach rate less than for copperamine treatment” we mean the leach rate using the AWPA test, determinedas percent of copper leached versus hours in wood samples, where onewood sample has the slurry of this invention and the comparative woodsample has a similar total copper loading from injected coppermonoethanolamine carbonate formulations, at 240 hours using thepreferred method of measuring leaching is with the AWPA Standard MethodE11-97 (1997), using a test extending to at least 300 hours duration.Another object of the invention is to provide an effective, injectablecopper-based particulate preservative treatment that retains more than94% of copper injected in a 14 day standard leach test.

Advantageously the copper-based particulate is an effectivepreservative. To be effective, the copper-based particles comprise oneor more sparingly soluble copper salts, and these salts must togetherrelease a small but effective concentration of soluble copper whenwetted with water. If the copper salts have too high a solubility, andthe copper is quickly leached out of the wood and contaminates theenvironment rather than protects the wood. Too low a solubility, and thecopper salts (and copper oxides) are not bioactive. The dissolutionrate/leach rate of the sparingly soluble copper salts used in theparticulates will be a function of 1) the solubility of the sparinglysoluble copper salt(s) in the leachant; 2) the surface area of thesparingly soluble copper salts available to contact the leachant, 3) theenergy of the crystal which must be overcome to dissolve ions from thecrystal lattice, and 4) the flow characteristics of the leachant in thewood matrix, especially regarding boundary layer effects. Each of theseproperties plays a role in every flowrate scenario, but some are moredominant than others at certain times. We believe the leach rates willbe primarily governed by the solubility of the sparingly soluble saltsand by boundary layer effects of the copper and counterions diffusingfrom the particulates in regimes where the leachant is moving extremelyslowly, e.g., less than a few millimeters per day. At intermediateleachant flow rates, we believe the leach rate of copper will depend onprimarily on the available surface area. At higher rates, such as foundin the standard test methods typically used by industry, the leach rateswill be governed more by the available surface area of the sparinglysoluble salts and by the energy of the crystal lattice.

Dissolution is a function not only of the pH of the water within thewood and the solubility product value for the particular salts, but alsoon dynamic conditions. Since the copper is present in the wood asparticulates, dissolution of copper will also be restricted by the lowsurface area of the particles. Larger particulates will reduce theleaching rate in most leachant flow regimes. The dissolution of largerparticulates is more dependent on surface effects than is thedissolution of smaller particulates, in part because the availablesurface area is lower for larger particulates. At low flow rates,boundary layer effects may multiply the effects of lower surface area,but at typical leach test flow regimes boundary layer effects may beminimized if the flow of the leachant through the wood matrix isturbulent.

At low flow rates, the p of the leachant will be modified by thedissolution of the copper hydroxides and the copper carbonates. Theisoelectric point of copper hydroxide is about 11, making copperhydroxide a very effective base. The presence of other basic salts, forexample phosphate ions, can further hinder leach rates. At high leachantflow rates, however, such as are used in standard leachant tests, theflow rates are such that the presence of hydroxides, phosphates, and thelike are minimized.

Since the leachant flow rates of wood in use can be highly variable, thecopper-based particulates advantageously provide a wide range ofcoverage over many environments by having 1) a wide distribution ofparticle sizes, 2) having sparingly soluble salts of differingsolubilities, or 3) both.

The biocidal compositions of this invention can be used in foliarapplications, in a variety of industrial applications, and in woodapplications. Generally, the biggest differences between foliarapplications and wood treatment are the particle size distribution mustbe narrower for injecting into wood than for spreading on fields. Acomposition having a d50 of 0.35 microns can be used in either a foliarapplication or a wood application. The advantages of excellent coverageand reduced treatment concentrations can be achieved if the d₉₀ iswithin about 3 times the d₅₀, and the d₉₉ can be any number. Unmilledcopper salts having a d₅₀ of 0.2 microns were useful for foliarapplications, and indeed that is the commercial purpose of thatformulation. For wood injection, on the other hand, the d₉₆ should beless that 3 times the d₅₀, preferably the d₉₈ is less that 3 times thed₅₀, more preferably the d₉₉ is less that 3 times the d₅₀. Additionally,different inorganic biocidal salts and different organic biocides may beselected for embodiments where the particles are exposed to sun andrain, versus those selected for the more protected environment withinwood.

Another aspect of the invention relates a method of preserving wood or awood product comprising injecting into wood or dispersing into a woodproduct one or more of the biocidal particulates of this invention. Thematerial of this invention is useful for wood, and also for woodproducts, e.g., wood composites. Exemplary wood products includeoriented strand board, particle board, medium density fiberboard,plywood, laminated veneer lumber, laminated strand lumber, hardboard andthe like. Preferred methods of preserving wood composites require thepreservatrive of this invention either be mixed with the wood materialor fibers before bonding, or more preferably injected into the woodmaterial or fibers, followed by bonding.

In one embodiment, the wood or wood product has a surface, a thickness,a width, and a length. Preferably, the wood or wood product comprises ahomogenous distribution of copper-based particles of the invention. Inone embodiment, a volume number density of the copper-based particles 5cm from the surface, and preferably throughout the interior of the woodor wood product, is at least about 50%, for example, at least about,60%, 70%, or 75% a volume number density of the copper-based particles 1cm from the surface.

Wood or wood products comprising copper-based particles in accordancewith the present invention may be prepared by subjecting the wood tovacuum and/or pressure in the presence of a flowable material comprisingthe copper-based particles. A pre-injection of carbon dioxide followedby vacuum and then injection of the slurry is a preferred method ofinjecting the slurry into wood. Injection of particles into the wood orwood product from a flowable material comprising the particles mayrequire longer pressure treatments than would be required for liquidsfree of such particles. Pressures of, for example, at least about 75psi, 100 psi, or 150 psi may be used. Exemplary flowable materialsinclude liquids comprising copper-based particles, emulsions comprisingcopper-based particles, and slurries comprising copper-based particles.

EXAMPLES

The following examples are merely indicative of the nature of thepresent invention, and should not be construed as limiting the scope ofthe invention, nor of the appended claims, in any manner.

Example 1 Milling Chlorothalonil with 0.5 mm Zirconium Silicate

The laboratory-sized vertical mill was provided by CB Mills, model#L-3-J. The mill has a 2 liter capacity and is jacketed for cooling.Unless otherwise specified, ambient water was cycled through the millcooling jacket during operation. The internal dimensions are 3.9″diameter by 9.1″ height. The mill uses a standard 3×3″ disk agitator(mild steel) on a stainless steel shaft, and it operates at 2,620 rpm.

The media used in this Example was 0.4-0.5 mm zirconium silicate beadssupplied by CB Mills. All particle size determinations were made with aSedigraph™ 5100T manufactured by Micromeritics, which uses x-raydetection and bases calculations of size on Stokes' Law.

The formulation contained 20.41% chlorothalonil (98% active), 5%Galoryl™ DT-120, 2% Morwet™ EFW, and 72.6% water by weight, and theconcentrate had a pH of 8.0. The total batch weight was about 600 g. Theresults of a 7.5 hour grinding study are given in Table 1 below. TABLE 1Particle Size Data - Volume % With Milling Time d₅₀ Diameter GreaterThan Mins. μm 10 μm 5 μm 2 μm 1 μm 0 4.9 10 48 95 30 1.3 0 4 21 68 601.0 4 2 11 50 90 1.4 18 23 22 94 120 1.03 2 0 4 150 1.12 0 2 6 58 1801.07 2 2 7 53 270 1.09 2 0 8 54 450 1.15 12 8 21 56

The results show that chlorothalonil can be wet milled from a startingparticle size of about 3-4 microns to a d₅₀ near 1 micron within aboutone hour, using a spherical ˜3.8 g/cm³ zirconium silicate media havingan average particle size of about 0.4-0.5 mm. Further grinding hadlittle effect, possibly slightly reducing the weight of particles overabout 2 microns and thereby reducing the d₉₀ from about 2 microns at 60minutes to slightly less than 2.

However, these results also showed the limitations of this lower densitymaterial. In the next example, higher density doped zirconia, having adensity of 5.5 to 6.5 g/cc, was used and provided much more effectivemilling.

Example 2 Milling Chlorothalonil with 0.5 mm Zirconium Oxide

The same mill and conditions were used in this experiment as inexperiment 1. However, the grinding media was 0.5-0.6 mm cerium-dopedzirconium oxide beads obtained from CB Mills. The density of the ceriumdoped zirconium oxide is ˜6.0 g/cm³. The formulation contained 20.41%chlorothalonil (98% Active), 5% Galoryl™ DT-120, 2% Morwet™ EFW, 3%Pluronic™ F-108, and 69.6% water by weight, and the concentrate had a pHof about 7.3. The total batch weight was about 600 g. The results areshown in Table 2 below. TABLE 2 Particle Size Data - Volume % WithMilling Time d₅₀ Diameter Greater Than Mins. μm 10 μm 5 μm 2 μm 1 μm 0.4μm 0.2 μm 0 3.44 8 30 77 92 — — 90 0.31 3 3 3 3 22 — 240 0.21 0 1 2 3 351

For the higher density 0.5 mm zirconia milling media, a composition witha d₅₀ less than 1 micron and a d₉₅ less than 1 micron was obtainable in90 minutes, and a composition with a d₅₀ less than 0.3 microns and a d₉₅less than 0.4 microns was obtainable in 6 hours. The product obtainedafter 90 minutes of milling represents an increase in number ofparticles per unit of mass by a factor of more than about 30 over thestandard products, but the product obtained after 90 minutes of millingrepresents an increase in number of particles per unit of mass by afactor of more than about 1000 over the standard products. The highersurface areas associated with the smaller particles should give rise toa product with enhanced bioactivity due to an increase in reservoiractivity (ability to deliver chlorothalonil to the infection court).

Example 3 Milling Sparingly Soluble Copper Salts with 0.5 mm ZirconiumSilicate

This comparative example and subsequent example show the effectivenessof the milling media and process on the particle size distribution ofinorganic copper salts.

Comparative Example 3A

A commercially available a magnesium stabilized form of copper hydroxideparticulate material, Champ DP® available from available fromPhibro-Tech., Inc., has particles with a d₅₀ of about 0.2 microns. FIG.3 shows the results of trying to inject untreated 2.5 micron d₅₀ copperhydroxide into wood. The copper material plugged the surface of the woodand made an unsightly blue-green stain. The results were less dramaticwhen injecting Champ DP, but were still commercially unacceptable.Analysis of the material found that while the d50 of the material was<0.2 microns, about 13% by weight of the material had diameters between2 and 5 times greater than the d₅₀, and 1% had an even greater diameter.

The Champ DP® material was placed in a mill with about a 50% by volumeloading of 2 mm zirconium silicate milling beads. Samples were removedintermittently and the particle size distribution was determined. Wetmilling with 2 mm zirconium silicate milling media had no effect—wetmilling for days resulted in only a very slight decrease in particlesize, a small shift in the particle size distribution, but the materialwas not injectable into wood

In contrast, five samples of particulate copper salts made followingstandard procedures known in the art were milled according to the methodof this invention. The first two samples were copper hydroxide—one withan initial particle size d₅₀ of <0.2 microns (the material ofcomparative example A), and the second with an initial d₅₀ of 2.5microns. A basic copper carbonate (BCC) salt was prepared and it had aninitial d₅₀ of 3.4 microns. A tribasic copper sulfate salt was preparedand this material has a d₅₀ of 6.2 micron. Finally, a copper oxychloride(COc) sample was prepared and this material has an initial d₅₀ of 3.3microns. Selected surface active agents were added to each slurry, andthe initial slurries were each in turn loaded into a ball mill having0.5 mm zirconium silicate (density 3.8 grams/cm3) at about 50% of millvolume, and milled at about 2600 rpm for about a half an hour. Theparticle size distribution of the milled material was then determined.The particle size distribution data is shown in Table 1. It can be seenthat even with the relatively modest zirconium silicate milling media,injectable compositions were obtained in about 30 minutes milling timeor less. TABLE 1 Particle Size Distribution Before/After Milling (0.5 mmZirconium Silicate) % < % < % < % < Material d50 10μ 1μ 0.4μ 0.2μCu(OH)₂, before milling <0.2 99% 84% 64% 57% Cu(OH)₂, after milling <0.299% 97% 95% 85% Cu(OH)2, before milling 2.5 99%  9% — — Cu(OH)2, aftermilling 0.3 99.7%   95% 22% —% BCC*, before milling 3.4 98% 1.2%  — —BCC*, after milling 0.2 99% 97% 97% 87% TBS*, before milling 6.2 70% 17%— — TBS*, after milling <0.2 99.5%   96% 91% 55% COc*, before milling3.3 98.5%    3% — — COc*, after milling 0.38 99.4%   94% 63% —

It can be seen that even the less effective milling media, ˜0.5 mmzirconium silicate, was useful for milling sparingly soluble coppersalts to the sub-micron particle size distribution needed for treatingwood, for incorporating into non-fouling paints and coatings, and forfoliar treatments. Further, the rate of particle size attrition is sogreat that there is no need to use expensive precipitation techniques toprovide a feedstock having a sub-micron d₅₀. The initial d50 ranged from0.2 microns to over 6 microns, but after 30 minutes or less of millingeach of the above milled copper salts (milling about 15 to about 30minutes) were injected into wood samples with no discernible plugging.

Milling with the more preferred zirconium oxide milling beads willprovide a smaller d50 and will further reduce the amount of material, ifany, having a diameter greater than 1 micron. Particulate biocides havean advantage over dispersed or soluble biocides in that the materialleaches more slowly from wood than would comparable amounts of solublebiocides, and also about the same or more slowly than comparable amountsof the same biocide applied to the same wood as an emulsion.

Example 4 Injecting Milled Copper Salt Slurries Into Wood

Slurries of the above milled sparingly soluble copper salts weresuccessfully injected into standard 1″ cubes of Southern Yellow Pinewood. The injection procedures emulated standard conditions used in theindustry.

FIG. 3 shows representative photographs showing the comparison of theunacceptable product, which had a d₅₀ of 2.5 microns yet still pluggedthe wood, is shown in comparison with blocks injected with the productmilled according to the process of this invention as described inExample 3. FIG. 3 shows the clean appearance of the wood blocks injectedwith the milled copper hydroxide, to compare with the photograph of thewood samples injected with the un-milled (d₅₀<0.2 micron) copperhydroxide. Unlike the blocks injected with un-milled material, woodblocks injected with milled material showed little or no color orevidence of injection of copper-containing particulate salts.

Copper development by colorimetric agents (dithio-oxamide/ammonia)showed the copper to be fully penetrated across the block in the sapwoodportion. FIG. 1 shows the penetration of injected particulate copperhydroxide developed with dithio-oxamide in the third picture. The staincorresponds to copper. It can be seen in FIG. 1 that the copper isevenly dispersed throughout the wood. Subsequent acid leaching andquantitative analysis of the copper from two blocks showed that loadingsof about 95% and about 104% of expectation (or essentially 100% averageof expectation) had occurred. At 100% loading, values of 0.22 lb/ft³ ofcopper would be obtained.

Example 5 Leaching Copper from Treated Wood

Copper leaching rates from the wood samples prepared in Example 4 weremeasured following the AWPA Standard Method E11-97. There are twocomparative examples—leaching data was obtained from a wood blockpreserved with a prior art soluble solution of copper MEA carbonate andfrom a prior art wood block preserved with CCA. The leach rates of thevarious wood blocks treated with the preservatives prepared according tothis invention were far below the leach rates of wood treated withsoluble copper carbonate and were even below leach rates of samplestreated with CCA.

Leaching data from wood was measured following the AWPA Standard MethodE11-97 for the following preservative treatments, where, unlessspecified, the tebuconazole (TEB) concentration was added as an emulsionat 3% of the weight of the added copper: A) TEB and injected basiccopper carbonate particulates; B) traditionally CCA-treated wood (as acontrol); C) TEB and copper methanolamine carbonate (as a control,believed to approximate the currently available Wolman E treatment); D)TEB and injected basic copper carbonate particulates and with sodiumbicarbonate buffer; E) Injected basic copper carbonate particulates; F)TEB and injected copper hydroxide particulates modified with zinc andmagnesium; G) about 5% TEB and injected copper hydroxide particulatesmodified with phosphate coating; H) TEB and injected tribasic coppersulfate particulates; and I) TEB and injected copper oxychlorideparticulates. The leaching data for the various particulate slurries andfrom two controls are shown in FIG. 2.

The total copper leached from wood preserved with copper-MEA-carbonatewas 5.7% at 6 hours, 8.5% at 24 hours, 11% at 48 hours, 22% at 96 hours,36% at 144 hours, 49% at 192 hours, 62% at 240 hours, 69% at 288 hours,and 76% at 336 hours. The amount of copper leached from copper hydroxideparticulates was 0.4% at 6 hours, 0.6% at 24 hours, 0.62% at 48 hours,1.0% at 96 hours, 1.6% at 144 hours, 2.1% at 192 hours, 3.2% at 240hours, 3.4% at 288 hours, and 3.7% at 336 hours. The difference in leachrate was greater than a factor of 20.

The leaching data is generally consistent within the small amount ofcopper leached from these wood samples. Using the copper leach rate ofCCA as a standard, and viewing the total leached copper at 96 and 240hours as representative, the leach rate ratios given by the “totalleached copper to total CCA-leached copper” is given in Table 3 below.

Of the sparingly soluble salts used, the leach rate, in descendingorder, is as follows: copper MEA carbonate (comparative)>>copperoxychloride>tribasic copper sulfate and/or copper hydroxide withphosphate>basic copper carbonate>copper hydroxide with Zn and Mg. Theisoelectric point of copper oxychloride is about 5 to about 5.5, and theisoelectric point of tribasic copper sulfate is about 6 to about 6.5. Asthese materials are very poor bases, the higher leach rates from thematerials is consistent with expected higher solubility at lower pHvalues. The presence of TEB reduced leach rates from basic coppercarbonate by about 20%, most likely due to TEB partially coatingparticulates. A buffering system, sodium bicarbonate, reduced the leachrates from TEB/basic copper carbonate by about 10% relative to apreservative without the buffer.

Use of the small diameter milling material, preferably 0.3 mm to 0.6 mm,is essential to make a product that can be confidently sold forinjection into wood.

Example 5 Toxicity Test

A sample of treated wood was sent to an outside source forshort-duration toxicity testing. The results suggest there is nodifference in the Threshold Toxicity between wood treated with a copperMEA carbonate/tebuconazole formulation and wood treated with a identicalloading of basic copper carbonate particles of this invention admixed(and partially coated with) the same quantity of tebuconazole.

The invention is meant to be illustrated by these examples, but notlimited to these examples. TABLE 3 96 hr. 240 hr. ratio ratio Ex.Description of Preservative System to CCA to CCA A 3% TEB and basiccopper carbonate particulates 0.67:1 0.51:1 C 3% TEB and copper MEAcarbonate  5.2:1 3.85:1 (comparative) D 3% TEB and basic coppercarbonate particulates 0.54:1 0.46:1 with sodium bicarbonate buffer Ebasic copper carbonate particulates 0.77:1 0.63:1 F 3% TEB and copperhydroxide with Zn and Mg  0.2:1 0.19:1 particulates G 5% TEB and copperhydroxide particulates  1.0:1 0.88:1 modified with phosphate coating H3% TEB and tribasic copper sulfate particulates 0.96:1 0.88:1 I 3% TEBand copper oxychloride particulates  1.4:1 1.17:1

1. A method of preserving wood comprising the steps of A) providing anaqueous wood preservative slurry comprising: a plurality of injectablefirst particulates comprising at least 20% by weight of a sparinglysoluble copper salt, wherein the d₉₆ of these first particulates isabout 1 micron or less, meaning 96 percent of the total volume of thefirst particulates have a diameter of about 1 micron or less, the d₉₉ isabout 1.5 microns or less, meaning 99% of the total volume of the firstparticulates have a diameter equal to or less than about 1.5 microns;and the d₅₀ is greater than 0.02 microns, meaning 50% of the totalvolume of the first particulates have a diameter greater than 0.02microns; and B) injecting the aqueous wood preservative slurry intowood.
 2. The method of claim 1, wherein the d₅₀ is between about 0.05microns and about 0.5 microns, meaning 50% of the total volume of thefirst particulates have a diameter equal to or less than a value betweenabout 0.05 microns and about 0.5 microns.
 3. The method of claim 1,wherein the d₅₀ is between about 0.1 microns and about 0.3 microns,meaning 50% of the total volume of the first particulates have adiameter equal to or less than a value between about 0.1 microns andabout 0.3 microns.
 4. The method of claim 2, wherein the sparinglysoluble copper salt comprises copper borate.
 5. The method of claim 1,wherein the sparingly soluble copper salt comprises copper borate and atleast one of basic copper carbonate or copper hydroxide, whereindifferent particulates can one or more of the three listed copper salts.6. The method of claim 2, wherein the sparingly soluble copper saltcomprises basic copper carbonate.
 7. The method of claim 2, wherein thesparingly soluble copper salt comprises copper hydroxide.
 8. The methodof claim 7, wherein the copper hydroxide comprises between 6 parts and20 parts magnesium per 100 parts copper.
 9. The method of claim 7,wherein the copper hydroxide comprises between 6 parts and 20 parts zincper 100 parts copper.
 10. The method of claim 1, wherein the sparinglysoluble copper salt comprises tribasic copper sulfate, copperoxychloride, basic copper nitrate, basic copper phosphate, basic copperphosphosulfate, or combinations thereof.
 11. The method of claim 1,wherein the sparingly soluble copper salt comprises copper ferricyanide,copper ferricyanate, copper carbonate, copper borate, copper silicate,copper fluorosilicate, copper thiocyanate, copper boride, or mixturethereof.
 12. The method of claim 2, wherein at least a portion of thefirst particulates comprise Cu₂O.
 13. The method of claim 1, wherein d₉₆of these first particulates is about 0.5 micron or less, meaning 96percent of the total volume of the first particulates have a diameter ofabout 0.5 micron or less, the d₉₉ is about 1 microns or less, meaning99% of the total volume of the first particulates have a diameter equalto or less than about 1 micron; and the d₅₀ is between 0.05 microns and0.4 microns, meaning 50% of the total volume of the first particulateshave a diameter equal to or less than a value between 0.05 microns andabout 0.4 microns.
 14. The method of claim 1, wherein the injectablefirst particulates had been wet-milled in the presence of a liquidcomprising a surface active agent and an effective amount of millingbeads having a diameter between 0.1 mm and 0.8 mm and a density greaterthan about 3 grams/cm³.
 15. The method of claim 1, wherein the aqueouswood preservative slurry further comprises a substantially insolubleorganic biocide, wherein at least a portion of the substantiallyinsoluble organic biocide is coated on the first particulates.
 16. Themethod of claim 1, wherein the aqueous wood preservative slurry furthercomprises a substantially insoluble organic biocide selected frombiocidal quaternary ammonium compounds; biocidal azoles; biocidaltriazoles, and moldicides, wherein at least 20% by weight of thesubstantially insoluble organic biocide is coated on the firstparticulates.
 17. The method of claim 1, wherein the aqueous woodpreservative slurry further comprises a plurality of injectable secondparticulates comprising at least 20% by weight of an injectable solidsubstantially insoluble organic biocide, wherein the d₉₆ of these secondparticulates is about 1 micron or less, meaning 96 percent of the totalvolume of the second particulates have a diameter of about 1 micron orless, and the d₉₀ is about 1.5 microns or less, meaning 99% of the totalvolume of the second particulates have a diameter equal to or less thanabout 1.5 microns.
 18. The method of claim 17, wherein the d₉₆ of thesesecond particulates is about 0.5 micron or less, meaning 96 percent ofthe total volume of the second particulates have a diameter of about 0.5micron or less, and the the d₅₀ is between about 0.05 microns and about0.4 microns, meaning 50% of the total volume of the second particulateshave a diameter equal to or less than a value between about 0.05 micronsand about 0.4 microns.
 19. The method of claim 17, wherein theinjectable second particulates had been wet-milled in the presence of aliquid comprising a surface active agent and an effective amount ofmilling beads having a diameter between 0.1 mm and 0.8 mm and a densitygreater than about 5.5 grams/cm³.
 20. The method of claim 1, wherein theaqueous wood preservative slurry further comprises third particulatescomprising at least 20% by weight of a sparingly soluble zinc salt, zincoxide, iron oxide, or any mixture thereof, wherein the d₉₆ of the thirdparticulates is about 1 micron or less, meaning 96 percent of the totalvolume of the third particulates have a diameter of about 1 micron orless, and the d₉₉ is about 1.5 microns or less, meaning 99% of the totalvolume of the third particulates have a diameter equal to or less thanabout 1.5 microns.
 21. A method of preserving wood comprising the stepsof A) providing an aqueous wood preservative slurry comprising: aplurality of injectable first particulates comprising at least 20% byweight of a sparingly soluble copper salt, of a sparingly soluble zincsalt, of a substantially insoluble organic biocide, or any combinationthereof, wherein the d₉₆ of the first particulates is about 1 micron orless, meaning 96 percent of the total volume of the first particulateshave a diameter of about 1 micron or less, the d₉₉ is about 1.5 micronsor less, meaning 99% of the total volume of the first particulates havea diameter equal to or less than about 1.5 microns; and the d₅₀ isgreater than 0.02 microns, meaning 50% of the total volume of the firstparticulates have a diameter greater than 0.02 microns; and B) injectingthe aqueous wood preservative slurry into wood.
 22. The method of claim21, wherein the d₅₀ is between about 0.05 microns and about 0.5 microns,meaning 50% of the total volume of the first particulates have adiameter equal to or less than a value between about 0.05 microns andabout 0.5 microns.
 23. The method of claim 21, wherein the d₅₀ isbetween about 0.1 microns and about 0.3 microns, meaning 50% of thetotal volume of the first particulates have a diameter equal to or lessthan a value between about 0.1 microns and about 0.3 microns.
 24. Themethod of claim 21, wherein the first particulates comprise one or moreof basic copper carbonate, copper hydroxide, copper hydroxide comprisingbetween 6 parts and 20 parts magnesium per 100 parts copper; copperhydroxide comprising between 6 parts and 20 parts magnesium per 100parts copper, copper hydroxide comprising 0.1 to 5% copper phosphate,tribasic copper sulfate, copper oxychloride, basic copper nitrate, basiccopper phosphate, basic copper phosphosulfate, or combinations thereof.25. The method of claim 24, wherein d₉₆ of these first particulates isabout 0.5 micron or less, meaning 96 percent of the total volume of thefirst particulates have a diameter of about 0.5 micron or less, the d₉₉is about 1 microns or less, meaning 99% of the total volume of the firstparticulates have a diameter equal to or less than about 1 micron; andthe d₅₀ is between 0.05 microns and 0.4 microns, meaning 50% of thetotal volume of the first particulates have a diameter equal to or lessthan a value between 0.05 microns and about 0.4 microns.
 26. The methodof claim 21, wherein the first particulates comprise one or more ofcopper ferricyanide, copper ferricyanate, copper carbonate, copperborate, copper silicate, copper fluorosilicate, copper thiocyanate,copper boride, or combinations thereof.
 27. The method of claim 21,wherein the first particulates comprise one or more of zinc hydroxide;basic zinc carbonate, basic zinc phosphate, zinc borate, or combinationsthereof.
 28. The method of claim 27, wherein d₉₆ of these firstparticulates is about 0.5 micron or less, meaning 96 percent of thetotal volume of the first particulates have a diameter of about 0.5micron or less, the d₉₉ is about 1 microns or less, meaning 99% of thetotal volume of the first particulates have a diameter equal to or lessthan about 1 micron; and the d₅₀ is between 0.05 microns and 0.4microns, meaning 50% of the total volume of the first particulates havea diameter equal to or less than a value between 0.05 microns and about0.4 microns.
 29. The method of claim 27, wherein the first particulatescomprise zinc borate.
 30. The method of claim 27, wherein the aqueouswood preservative slurry further comprises a substantially insolubleorganic biocide, wherein at least a portion of the substantiallyinsoluble organic biocide is coated on the first particulates.
 31. Themethod of claim 27, wherein the aqueous wood preservative slurry furthercomprises a substantially insoluble organic biocide selected frombiocidal quaternary ammonium compounds; biocidal azoles; biocidaltriazoles, and moldicides, wherein at least 20% by weight of thesubstantially insoluble organic biocide is coated on the firstparticulates.
 32. The method of claim 21, wherein the first particulatescomprise one or more of zinc oxychloride; zinc fluoroborate, zinccarbonate, zinc orthophosphate, zinc fluoride, or combinations thereof.33. The method of claim 32, wherein the aqueous wood preservative slurryfurther comprises a substantially insoluble organic biocide, wherein atleast a portion of the substantially insoluble organic biocide is coatedon the first particulates.
 34. The method of claim 32, wherein theaqueous wood preservative slurry further comprises a plurality ofinjectable second particulates comprising at least 20% by weight of aninjectable solid substantially insoluble organic biocide, wherein thed₉₆ of these second particulates is about 1 micron or less, meaning 96percent of the total volume of the second particulates have a diameterof about 1 micron or less, and the d₉₉ is about 1.5 microns or less,meaning 99% of the total volume of the second particulates have adiameter equal to or less than about 1.5 microns.
 35. The method ofclaim 21, wherein the first particulates comprise solid substantiallyinsoluble organic biocides, wherein the injectable first particulateshad been wet-milled in the presence of a liquid comprising a surfaceactive agent and an effective amount of milling beads having a diameterbetween 0.1 mm and 0.8 mm and a density greater than about 3.5grams/cm³.
 36. The method of claim 35, wherein the solid substantiallyinsoluble organic biocides comprises one or more of Chlorothalonil,Metaldehyde, triphenyltin hydroxide, Maneb, Mancozeb, Zineb, Ziram, andFerbam.
 37. The method of claim 35, wherein the solid substantiallyinsoluble organic biocides comprises one or more of biocidal solidimidazolinones, sulfonylureas, triazolopyrimidine sulfonamides,aryloxyphenoxy propionates, triazines, chloroacetanilides, pyrazoles,and diphenyl ethers.
 38. The method of claim 35, wherein the solidsubstantially insoluble organic biocides comprises one or more ofamitraz, azinphos-ethyl, azinphos-methyl, benzoximate, fenobucarb,gamma-HCH, methidathion, deltamethrin, dicofol, dioxabenzafos,dioxacarb, dinobuton, endosulfan, bifenthrin, binapacryl, bioresmethrin,chlorpyrifos, chlorpyrifos-methyl, EPNethiofencarb, cyanophos,cyfluthrin, tetradifon, cypermethrin, tralomethrin, bromophos,N-2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene-xylidene, 2,4-parathionmethyl, bromopropylate, butacarboxim, butoxycarboxin, chlordimeform,phosalone, chlorobenzilate, phosfolan, chloropropylate, phosmet,chlorophoxim, promecarb, fenamiphos, quinalphos, resmethrin, temephos,pirimiphos-ethyl, tetramethrin, pirimiphos-methyl, xylylcarb,profenofos, acrinathrin, propaphos, allethrin, propargite, benfuracarb,propetamphos, bioallethrin, pyrachlofos, bioallethrin S, tefluthrin,bioresmethrin, terbufos, buprofezin, tetrachlorinphos, chlorfenvinphos,tralomethrin, chlorflurazuron, triazophos, chlormephos, pyrachlofos,tefluthrin, terbufos, tetrachlorinphos, cycloprothrin, betacyfluthrin,cyhalothrin, cambda-cyhalothrin, tralomethrin, alpha-cypermethrin,triazophos, beta-cypermethrin, cyphenothrin, demeton-S-methyl,dichlorvos, disulfoton, edifenphos, empenthrin, esfenvalerate,ethoprophos, etofenprox, etrimphos, fenazaquin, fenitrothion,fenthiocarb, fenpropathrin, fenthion, fenvalerate, flucythrinate,flufenoxuron, tau-fluvalinate, formothion, hexaflumuron, hydroprene,isofenphos, isoprocarb, isoxathion, malathion, mephospholan, methoprene,methoxychlor, mevinphos, permethrin, phenothrin, phenthoate, benalaxyl,biteranol, bupirimate, cyproconazole, carboxin, tetraconazole,dodemorph, difenoconazole, dodine, dimethomoph, fenarimol, diniconazole,ditalimfos, ethoxyquin, myclobutanil, etridiazole, nuarimol,fenpropidin, oxycarboxin, fluchloralin, penconazole, flusilazole,prochloraz, imibenconazole, tolclofos-methyl, myclobutanil, triadimefon,propiconazole, triadimenol, pyrifenox, azaconazole, tebuconazole,epoxyconazole, tridemorph, fenpropimorph, triflumizole, 2,4-D esters,diclofop-methyldiethatyl, 2,4-DB esters, dimethachlor, acetochlor,dinitramine, aclonifen, ethalfluralin, alachlor, ethofumesate,anilophos, fenobucarb, benfluralin, fenoxapropethyl, benfuresate,fluazifop, bensulide, fluazifop-P, benzoylprop-ethyl, fluchloralin,bifenox, flufenoxim, bromoxynil esters, flumetralin, bromoxynil,flumetralin, butachlor, fluorodifen, butamifos, fluoroglycofen ethyl,butralin, fluoroxypyr esters, butylate, carbetamide, chlornitrofen,chlorpropham, cinmethylin, clethodim, clomazone, clopyralid esters, CMPPesters, cycloate, cycloxydim, desmedipham, dichlorprop esters, flurecolbutyl, flurochloralin, haloxyfop, ethoxyethyl, haloxyfop-methyl, ioxynilesters, isopropalin, MCPA esters, mecoprop-P esters, metolachlor,monalide, napropamide, nitrofen, oxadiazon, oxyfluorfen, phenisopham,phenmedipham, picloram esters, pretilachlor, profluralin, propachlor,propanil, propaquizafop, pyridate, quizalofop-P, triclopyr esters, andtridiphane.
 39. The method of claim 35, wherein the solid substantiallyinsoluble organic biocides comprises one or more of diuron,chlorotoluron, simazine, atrazine, carbendazime, maneb, mancozeb, fentinhydroxide, and endosulfan.
 40. The method of claim 39, wherein theinjectable first particulates had been wet-milled in the presence of aliquid comprising a surface active agent and an effective amount ofmilling media, wherein at least 25% by weight of the milling mediacomprises milling beads having a diameter between 0.2 mm and 0.7 mm anda density greater than about 5.5 grams/cm³.
 41. The method of claim 35,wherein the solid substantially insoluble organic biocides comprises oneor more of chlorothalonil, copper thiocyanate, zinc pyrithione, and4,5-dicholo-2-n-octyl-4-isothiazolin-3-one.
 42. The method of claim 41,wherein the injectable first particulates had been wet-milled in thepresence of a liquid comprising a surface active agent and an effectiveamount of milling media, wherein at least 25% by weight of the millingmedia comprises milling beads having a diameter between 0.2 mm and 0.7mm and a density greater than about 5.5 grams/cm³.
 43. The method ofclaim 35, wherein the aqueous wood preservative slurry further comprisesa second substantially insoluble organic biocide, wherein at least aportion of the second substantially insoluble organic biocide is coatedon the first particulates.
 44. The method of claim 21, wherein the firstparticulates comprise zinc carbonate, wherein the aqueous woodpreservative slurry further comprises a plurality of injectable secondparticulates comprising at least 20% by weight of one or more of zinchydroxide, copper hydroxide, copper borate, basic copper carbonate, ormixture thereof.
 45. A method of preserving wood comprising the steps ofA) providing an aqueous wood preservative slurry comprising: a pluralityof injectable first particulates comprising one or more of copper(I)oxide, a sparingly soluble copper salt, zinc oxide, a sparingly solublezinc salt, iron oxide, a first solid substantially insoluble organicbiocide, or any combination thereof, wherein the d₉₆ of the firstparticulates is about 1 micron or less, meaning 96 percent of the totalvolume of the first particulates have a diameter of about 1 micron orless, the d₉₉ is about 1.5 microns or less, meaning 99% of the totalvolume of the first particulates have a diameter equal to or less thanabout 1.5 microns; and the d₅₀ is greater than 0.02 microns, meaning 50%of the total volume of the first particulates have a diameter greaterthan 0.02 microns, wherein the first particulates comprise a secondsubstantially insoluble organic biocide disposed on the surface of thefirst particulates, wherein the second substantially insoluble organicbiocide is different from the first substantially insoluble organicbiocide, if any; and B) injecting the aqueous wood preservative slurryinto wood.
 46. The method of claim 45, wherein the d₉₆ of these secondparticulates is about 0.5 micron or less, meaning 96 percent of thetotal volume of the second particulates have a diameter of about 0.5micron or less, and the the d₅₀ is between about 0.05 microns and about0.4 microns, meaning 50% of the total volume of the second particulateshave a diameter equal to or less than a value between about 0.05 micronsand about 0.4 microns.
 47. The method of claim 45, wherein theinjectable first particulates had been wet-milled in the presence of aliquid comprising a surface active agent and an effective amount ofmilling media, wherein at least 25% by weight of the milling mediacomprises milling beads having a diameter between 0.2 mm and 0.7 mm anda density greater than about 5.5 grams/cm³.